Novel herbicides

ABSTRACT

Compounds of formula (I), wherein the substituents are as defined in claim  1 , and the agrochemically acceptable salts and all stereoisomers and tautomeric forms of the compounds of formula I are suitable for use as herbicides.

The present invention relates to novel, herbicidally active nicotinoyl derivatives, to processes for their preparation, to compositions comprising those compounds, and to their use in controlling weeds, especially in crops of useful plants, or in inhibiting plant growth.

Nicotinoyl derivatives having herbicidal action are described, for example, in WO 00/15615 and WO 01/94339.

There have now been found novel nicotinoyl derivatives having herbicidal and growth-inhibiting properties, the structures of which are distinguished by a double bond in the 6,7-position of the bicyclo[3.2.1]oct-3-en-2-one, bicyclo[3.2.1]nona-3-en-2-one, 8-oxa-bicyclo-[3.2.1]octa-3-en-2-one, 8-aza-bicyclo[3.2.1]octa-3-en-2-one, 8-thia-bicyclo[3.2.1]octa-3-en-2-one and bicyclo[3.2.1]octa-3-ene-2,8-dione group. Some of the compounds of that kind are covered by WO 00/15615 but none of those compounds is specifically disclosed. WO 01/66522 includes pyridine ketones having bicyclo[3.2.1]oct-3-en-2-one groups as intermediates in the preparation of aroyl ketones. There is no mention therein of those compounds having a herbicidal action.

The present invention accordingly relates to compounds of formula I

wherein

-   Y is oxygen, NR_(4a), sulfur, sulfonyl, sulfinyl, C(O), C(═NR_(4b)),     C(═CR_(6a)R_(6b)) or a C₁-C₄alkylene or C₂-C₄alkenylene chain, which     may be interrupted by oxygen, NR_(5a), sulfur, sulfonyl, sulfinyl,     C(O) or C(═NR_(5b)) and/or mono- or poly-substituted by R₆; -   A₁ is nitrogen or CR₇; -   A₂ is nitrogen or CR₈; -   R₁, R₂, R₆, R₇ and R₈ are each independently of the others hydrogen,     hydroxy, mercapto, NO₂, cyano, halogen, formyl, oxyiminomethylene,     C₁-C₆alkoxyiminomethylene, C₁-C₆alkyl, C₁-C₆haloalkyl, C₂-C₆alkenyl,     C₂-C₆haloalkenyl, C₂-C₆alkynyl, C₂-C₆haloalkynyl, C₁-C₆alkoxy,     C₁-C₆haloalkoxy, C₃-C₆alkenyloxy, C₃-C₆alkynyloxy,     C₃-C₆oxacycloalkyl, C₃-C₆thiacycloalkyl, C₃-C₆dioxacycloalkyl,     C₃-C₆dithiacycloalkyl, C₃-C₆oxathiacycloalkyl, C₁-C₆alkoxycarbonyl,     C₁-C₆alkylcarbonyl, C₁-C₆alkoxycarbonyloxy, C₁-C₆alkylcarbonyloxy,     C₁-C₆alkylthio, C₁-C₆alkylsulfonyl, C₁-C₆alkylsulfinyl, NR₉R₁₀,     C₃-C₆cycloalkyl, tri(C₁-C₆alkyl)silyl, di(C₁-C₆alkyl)phenylsilyl,     tri(C₁-C₆alkyl)silyloxy, di(C₁-C₆alkyl)phenylsilyloxy or Ar₁; -   or R₁, R₂, R₆, R₇, R₈ are each independently of the others a     C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl or C₃-C₆cycloalkyl group,     which may be interrupted by oxygen, sulfur, sulfonyl, sulfinyl,     —NR₁₁— or —C(O)— and/or mono-, di- or tri-substituted by hydroxy,     mercapto, NO₂, cyano, halogen, formyl, C₁-C₆alkoxy, C₃-C₆alkenyloxy,     C₃-C₆alkynyloxy, C₁-C₆haloalkoxy, C₁-C₂alkoxy-C₁-C₂alkoxy,     C₁-C₄alkoxycarbonyloxy, C₁-C₄alkylcarbonyloxy, C₁-C₄alkoxy-carbonyl,     C₁-C₄alkylcarbonyl, C₁-C₆alkylthio, C₁-C₆alkylsulfinyl,     C₁-C₆alkylsulfonyl, NR₁₂R₁₃, C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl,     C₃-C₆cycloalkyl, tri(C₁-C₆alkyl)silyl, tri(C₁-C₆alkyl)-silyloxy or     Ar₂; -   or two substituents R₆ at the same carbon atom together form a     —CH₂O— or a C₂-C₅alkylene chain, which may be interrupted once or     twice by oxygen, sulfur, sulfinyl or sulfonyl and/or mono- or     poly-substituted by R_(6c), with the proviso that two hetero atoms     may not be located next to one another; -   or two substituents R₆ at different carbon atoms together form an     oxygen bridge or a C₁-C₄alkylene chain, which may in turn be     substituted by R_(6c); -   or R₇ and R₈ together form a —CH₂CH═CH—, —OCH═CH— or —CH═CH—CH═CH—     bridge or a C₃-C₄alkylene chain, which may be interrupted by oxygen     or —S(O)_(n1)— and/or mono- or poly-substituted by R_(6d); -   R₃ is hydroxy, halogen, mercapto, C₁-C₈alkylthio,     C₁-C₈alkylsulfinyl, C₁-C₈alkylsulfonyl, C₁-C₈haloalkylthio,     C₁-C₈haloalkylsulfinyl, C₁-C₈haloalkylsulfonyl,     C₁-C₄alkoxy-C₁-C₄alkylthio, C₁-C₄alkoxy-C₁-C₄alkylsulfinyl,     C₁-C₄alkoxy-C₁-C₄alkylsulfonyl, C₃-C₈alkenylthio, C₃-C₈-alkynylthio,     C₁-C₄alkylthio-C₁-C₄alkylthio, C₃-C₄alkenylthio-C₁-C₄alkylthio,     C₁-C₄alkoxycarbonyl-C₁-C₄alkylthio,     C₁-C₄alkoxycarbonyl-C₁-C₄alkylsulfinyl,     C₁-C₄alkoxycarbonyl-C₁-C₄alkylsulfonyl, C₃-C₈cycloalkylthio,     C₃-C₈cycloalkylsulfinyl, C₃-C₈cycloalkylsulfonyl,     phenyl-C₁-C₄alkylthio, phenyl-C₁-C₄alkylsulfinyl,     phenyl-C₁-C₄alkylsulfonyl, S(O)n₁—Ar₃, phenylthio, phenylsulfinyl,     phenylsulfonyl, it being possible for the phenyl-containing groups     to be substituted by one or more C₁-C₃alkyl, C₁-C₃haloalkyl,     C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₄alkoxycarbonyl, halogen, cyano,     hydroxy or nitro groups; -   or R₃ is O⁻M⁺, wherein M⁺ is an alkali metal cation or an ammonium     cation; -   Q is a radical -   p₁, p₂ and p₃ are 0 or 1; -   m₁, m₂ and m₃ are 1, 2 or 3; -   X₁, X₂ and X₃ are hydroxy, halogen, C₁-C₆alkyl, C₁-C₆haloalkyl,     C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-C₆alkynyl, C₂-C₆haloalkynyl,     C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₁-C₆alkylthio, C₁-C₆alkylsulfinyl,     C₁-C₆alkylsulfonyl, C₁-C₆haloalkylthio, C₁-C₆haloalkylsulfinyl or     C₁-C₆haloalkylsulfonyl; -   Z₁, Z₂ and Z₃ are C₁-C₆alkyl which is substituted by the following     substituents: C₃-C₄cycloalkyl or C₃-C₄cycloalkyl substituted by     halogen, C₁-C₆alkyl, C₁-C₃alkoxy or C₁-C₃alkoxy-C₁-C₃alkyl; oxiranyl     or oxiranyl substituted by C₁-C₆alkyl or C₁-C₃alkoxy-C₁-C₃alkyl;     3-oxetanyl or 3-oxetanyl substituted by C₁-C₆alkyl, C₁-C₃alkoxy or     C₁-C₃alkoxy-C₁-C₃alkyl; 3-oxetanyloxy or 3-oxetanyloxy substituted     by C₁-C₆alkyl, C₁-C₃alkoxy or C₁-C₃alkoxy-C₁-C₃alkyl;     C₃-C₆cycloalkyloxy or C₃-C₄cycloalkyloxy substituted by halogen,     C₁-C₆alkyl, C₁-C₃alkoxy or C₁-C₃alkoxy-C₁-C₃alkyl; C₁-C₆haloalkoxy;     C₁-C₆alkylsulfonyloxy; C₁-C₆haloalkylsulfonyloxy; phenylsulfonyloxy;     benzylsulfonyloxy; benzoyloxy; phenoxy; phenylthio; phenylsulfinyl;     phenylsulfonyl; Ar₁₀; OAr₁₂; tri(C₁-C₆alkyl)silyl or     tri(C₁-C₆alkyl)silyloxy, it being possible for the phenyl-containing     groups to be mono- or poly-substituted by C₁-C₃alkyl,     C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano,     hydroxy or nitro; -   or Z₁, Z₂ and Z₃ are 3-oxetanyl; 3-oxetanyl substituted by     C₁-C₃alkoxy, C₁-C₃alkoxy-C₁-C₃-alkyl or C₁-C₆alkyl; C₃-C₆cycloalkyl     substituted by halogen, C₁-C₃alkyl or C₁-C₃alkoxy-C₁-C₃-alkyl;     tri(C₁-C₆alkyl)silyl; tri(C₁-C₆alkyl)silyloxy or CH═P(phenyl)₃; -   or Z₁, Z₂ and Z₃ are a C₁-C₆alkyl, C₂-C₆alkenyl or C₂-C₆alkynyl     group, which is interrupted by oxygen, —O(CO)—, —(CO)O—, —O(CO)O—,     —N(R₁₄)O—, —ONR₁₅—, sulfur, sulfinyl, sulfonyl, —SO₂NR₁₆—, —NR₁₇SO₂—     or —NR₁₈— and is mono- or poly-substituted by L₁; it also being     possible for L₁ to be bonded at the terminal carbon atom of the     C₁-C₆alkyl, C₂-C₆alkenyl or C₂-C₆alkynyl group; -   or Z₁, Z₂ and Z₃ are hydrogen, hydroxy, mercapto, NO₂, cyano,     halogen, formyl, C₁-C₆alkyl, C₁-C₆haloalkyl, C₂-C₆alkenyl,     C₂-C₆haloalkenyl, C₂-C₆alkynyl, C₂-C₆haloalkynyl, C₁-C₆alkoxy,     C₁-C₆haloalkoxy, C₁-C₆alkoxycarbonyl, C₁-C₆alkylcarbonyl,     C₁-C₆alkylthio, C₁-C₆alkylsulfonyl, C₁-C₆alkylsulfinyl, NR₂₂R₂₃,     phenyl which may be mono- or poly-substituted by C₁-C₃alkyl,     C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano,     hydroxy or nitro, C₃-C₆cycloalkyl, C₅-C₆cycloalkyl substituted by     C₁-C₃alkoxy, C₁-C₃alkoxy-C₁-C₃alkyl or C₁-C₆alkyl, or Ar₅, O—Ar₆,     N(R₂₄)Ar₇ or S(O)n₆Ar₈; -   L₁ is hydrogen, halogen, hydroxy, amino, formyl, nitro, cyano,     mercapto, carbamoyl, P(O)(OC₁-C₆alkyl)₂, C₁-C₆alkoxy,     C₁-C₆haloalkoxy, C₁-C₆alkoxycarbonyl, C₂-C₆alkenyl,     C₂-C₆haloalkenyl, C₂-C₆alkynyl, C₂-C₆haloalkynyl, C₃-C₆cycloalkyl,     halo-substituted C₃-C₆cycloalkyl, C₃-C₆alkenyloxy, C₃-C₆alkynyloxy,     C₃-C₆haloalkenyloxy, cyano-C₁-C₆alkoxy, C₁-C₆alkoxy-C₁-C₆alkoxy,     C₁-C₆alkylthio-C₁-C₆alkoxy, C₁-C₆alkylsulfinyl-C₁-C₆alkoxy,     C₁-C₆alkylsulfonyl-C₁-C₆alkoxy, C₁-C₆alkoxycarbonyl-C₁-C₆alkoxy,     C₁-C₆alkylcarbonyloxy-C₁-C₆alkylcarbonyl, C₁-C₆alkylthio,     C₁-C₆alkylsulfinyl, C₁-C₆alkylsulfonyl, C₁-C₆haloalkylthio,     C₁-C₆haloalkylsulfinyl, C₁-C₆haloalkylsulfonyl or oxiranyl, which     may in turn be substituted by C₁-C₆alkyl, C₁-C₃alkoxy or     C₁-C₃alkoxy-C₁-C₃alkyl, or (3-oxetanyl)-oxy, which may in turn be     substituted by C₁-C₆alkyl, C₁-C₃alkoxy or C₁-C₃alkoxy-C₁-C₃alkyl, or     benzoyloxy, benzyloxy, benzylthio, benzylsulfinyl, benzylsulfonyl,     C₁-C₆alkylamino, di(C₁-C₆alkyl)amino, R₁₉S(O)₂O—, R₂₀N(R₂₁)SO₂—,     rhodano, phenyl, phenoxy, phenylthio, phenylsulfinyl,     phenylsulfonyl, Ar₄ or OAr₁₁, it being possible for the     phenyl-containing groups in turn to be substituted by one or more     C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen,     cyano, hydroxy or nitro groups; -   R_(4a) and R_(5a) are each independently of the other hydrogen,     C₁-C₆alkyl, C₁-C₆haloalkyl, cyano, formyl, C₁-C₆alkylcarbonyl,     C₁-C₆alkoxycarbonyl, carbamoyl, C₁-C₆alkylaminocarbonyl,     di(C₁-C₆alkylamino)carbonyl, di(C₁-C₆alkylamino)sulfonyl,     C₃-C₆cycloalkylcarbonyl, C₁-C₆-alkylsulfonyl, phenylcarbonyl,     phenylaminocarbonyl or phenylsulfonyl, it being possible for the     phenyl groups to be mono- or poly-substituted by C₁-C₆alkyl,     C₁-C₆haloalkyl, C₁-C₆-alkoxy, C₁-C₆haloalkoxy, halogen, cyano,     hydroxy or nitro; -   R_(4b) and R_(5b) are each independently of the other hydroxy,     C₁-C₆alkoxy, C₃-C₆alkenyloxy, C₃-C₆alkynyloxy or benzyloxy, it being     possible for the benzyl group to be mono- or poly-substituted by     C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, halogen,     cyano, hydroxy or nitro; -   R₉, R₁₁, R₁₃, R₁₆, R₁₇, R₁₈, R₂₀, R₂₃ and R₂₄ are each independently     of the others hydrogen, C₁-C₆alkyl, Ar₉, C₁-C₆haloalkyl,     C₁-C₆alkylcarbonyl, C₁-C₆alkoxycarbonyl, C₁-C₆alkylsulfonyl, phenyl,     it being possible for the phenyl group in turn to be mono- or     poly-substituted by C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy,     C₁-C₆haloalkoxy, halogen, cyano, hydroxy or nitro; -   R_(6a) is hydrogen, C₁-C₆alkyl or C₁-C₆alkylcarbonyl; or together     with R_(6b) is a C₂-C₅alkylene chain; -   R_(6b), R_(6d), R₁₀, R₁₂ and R₂₂ are each independently of the     others hydrogen or C₁-C₆alkyl; -   R_(6c), R₁₄, R₁₅, R₁₉ and R₂₁ are each independently of the others     C₁-C₆alkyl or C₁-C₆haloalkyl; -   Ar₁, Ar₂, Ar₃, Ar₄, Ar₅, Ar₆, Ar₇, Ar₈, Ar₉, Ar₁₀, Ar₁₁ and Ar₁₂ are     each independently of the others a five- to ten-membered, monocyclic     or fused bicyclic ring system, which may be aromatic, partially     saturated or fully saturated and may contain from 1 to 4 hetero     atoms selected from nitrogen, oxygen, sulfur, C(O) and C(═NR₂₅), and     each ring system may contain not more than two oxygen atoms, not     more than two sulfur atoms, not more than two C(O) groups and not     more than one C(═NR₂₅) group, and each ring system may itself be     mono- or poly-substituted by C₁-C₆alkyl, C₁-C₆haloalkyl,     C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-C₆alkynyl, C₂-C₆haloalkynyl,     C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₃-C₆alkenyloxy, C₃-C₆alkynyloxy,     mercapto, amino, hydroxy, C₁-C₆alkylthio, C₁-C₆haloalkylthio,     C₃-C₆alkenylthio, C₃-C₆-haloalkenylthio, C₃-C₆alkynylthio,     C₁-C₃alkoxy-C₁-C₃alkylthio, C₁-C₄alkylcarbonyl-C₁-C₃alkylthio,     C₁-C₄alkoxycarbonyl-C₁-C₃alkylthio, cyano-C₁-C₃alkylthio,     C₁-C₆alkylsulfinyl, C₁-C₆haloalkylsulfinyl, C₁-C₆alkylsulfonyl,     C₁-C₆haloalkylsulfonyl, aminosulfonyl, C₁-C₂alkylaminosulfonyl,     N,N-di(C₁-C₂alkyl)aminosulfonyl, di(C₁-C₄alkyl)amino, halogen,     cyano, nitro or phenyl, it being possible for the phenyl group in     turn to be substituted by hydroxy, C₁-C₆-alkylthio,     C₁-C₆haloalkylthio, C₃-C₆alkenylthio, C₃-C₆haloalkenylthio,     C₃-C₆alkynylthio, C₁-C₃alkoxy-C₁-C₃alkylthio,     C₁-C₄alkylcarbonyl-C₁-C₃alkylthio,     C₁-C₄alkoxycarbonyl-C₁-C₃-alkylthio, cyano-C₁-C₃alkylthio,     C₁-C₆alkylsulfinyl, C₁-C₆haloalkylsulfinyl, C₁-C₆alkylsulfonyl,     C₁-C₆haloalkylsulfonyl, aminosulfonyl, C₁-C₂alkylaminosulfonyl,     N,N-di(C₁-C₂alkyl)aminosulfonyl, di(C₁-C₄alkyl)amino, halogen, cyano     or nitro, and the substituents at the nitrogen atom in the     heterocyclic ring being other than halogen, and two oxygen atoms not     being located next to one another; -   R₂₅ is hydrogen, hydroxy, C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy,     C₁-C₆alkylcarbonyl, C₁-C₆alkoxycarbonyl or C₁-C₆alkylsulfonyl; and -   n₁ is 0, 1 or 2; and n₆ is 0, 1 or 2; -   and agronomically acceptable salts/isomers/enantiomers/tautomers of     those compounds.

The alkyl groups appearing in the substituent definitions may be straight-chain or branched and are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl and octyl and the branched isomers thereof. Alkoxy, alkenyl and alkynyl radicals are derived from the mentioned alkyl radicals. The alkenyl and alkynyl groups may be mono- or poly-unsaturated. C₁-C₄alkylene and C₂-C₄alkenylene chains may likewise be straight-chain or branched.

Halogen is generally fluorine, chlorine, bromine or iodine, preferably fluorine or chlorine. The same is true of halogen in conjunction with other meanings, such as haloalkyl or halophenyl.

Haloalkyl groups preferably have a chain length of from 1 to 6 carbon atoms. Haloalkyl is, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl, 1,1-difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl or 2,2,2-trichloroethyl; preferably trichloromethyl, difluorochloromethyl, difluoromethyl, trifluoromethyl or dichlorofluoromethyl.

In the context of the present invention, the term “mono- or poly-substituted” is generally to be understood as meaning mono- to penta-substituted, especially mono- to tri-substituted.

As haloalkenyl there come into consideration alkenyl groups mono- or poly-substituted by halogen, halogen being fluorine, chlorine, bromine or iodine, and especially fluorine or chlorine, for example 2,2-difluoro-1-methylvinyl, 3-fluoropropenyl, 3-chloropropenyl, 3-bromopropenyl, 2,3,3-trifluoropropenyl, 2,3,3-trichloropropenyl and 4,4,4-trifluoro-but-2-en-1-yl. Of the C₃-C₈alkenyl groups mono-, di- or tri-substituted by halogen preference is given to those having a chain length of from 3 to 5 carbon atoms.

As haloalkynyl there come into consideration, for example, alkynyl groups mono- or poly-substituted by halogen, halogen being bromine, iodine and especially fluorine or chlorine, for example 3-fluoropropynyl, 3-chloropropynyl, 3-bromopropynyl, 3,3,3-trifluoropropynyl and 4,4,4-trifluoro-but-2-yn-1-yl. Of the alkynyl groups mono- or poly-substituted by halogen preference is given to those having a chain length of from 3 to 5 carbon atoms.

Ar₁, Ar₂, Ar₃, Ar₄, Ar₅, Ar₆, Ar₇, A₈, A₉, Ar₁₀, Ar₁₁ and Ar₁₂ are, for example, phenyl, naphthyl or the following heterocyclic groups: (1-methyl-1H-pyrazol-3-yl)-; (1-ethyl-1H-pyrazol-3-yl)-; (1-propyl-1H-pyrazol-3-yl)-; (1H-pyrazol-3-yl)-; (1,5-dimethyl-1H-pyrazol-3-yl)-; (4-chloro-1-methyl-1H-pyrazol-3-yl)-; (1H-pyrazol-1-yl)-; (3-methyl-1H-pyrazol-1-yl)-; (3,5-dimethyl-1H-pyrazol-1-yl)-; (3-isoxazolyl)-; (5-methyl-3-isoxazolyl)-; (3-methyl-5-isoxazolyl)-; (5-isoxazolyl)-; (1H-pyrrol-2-yl)-; (1-methyl-1H-pyrrol-2-yl)-; (1H-pyrrol-1-yl)-; (1-methyl-1H-pyrrol-3-yl)-; (2-furanyl)-; (5-methyl-2-furanyl)-; (3-furanyl)-; (5-methyl-2-thienyl)-; (2-thienyl)-; (3-thienyl)-; (1-methyl-1H-imidazol-2-yl)-; (1H-imidazol-2-yl)-; (1-methyl-1H-imidazol-4-yl)-; (1-methyl-1H-imidazol-5-yl)-; (4-methyl-2-oxazolyl)-; (5-methyl-2oxazolyl)-; (2-oxazolyl)-; (2-methyl-5-oxazolyl)-; (2-methyl-4-oxazolyl)-; (4-methyl-2-thiazolyl)-; (5-methyl-2-thiazolyl)-; (2-thiazolyl)-; (2-methyl-5-thiazolyl)-; (2-methyl-4-thiazolyl)-; (3-methyl-4-isothiazolyl)-; (3-methyl-5-isothiazolyl)-; (5-methyl-3-isothiazolyl)-; (1-methyl-1H-1,2,3-triazol-4-yl)-; (2-methyl-2H-1,2,3-triazol-4-yl)-; (4-methyl-2H-1,2,3-triazol-2-yl)-; (1-methyl-1H-1,2,4-triazol-3-yl)-; (1,5-dimethyl-1H-1,2,4-triazol-3-yl)-; (3-methyl-1H-1,2,4-triazol-1-yl)-; (5-methyl-1H-1,2,4-triazol-1-yl)-; (4,5-dimethyl-4H-1,2,4-triazol-3-yl)-; (4-methyl-4H-1,2,4-triazol-3-yl)-; (4H-1,2,4-triazol-4-yl)-; (5-methyl-1,2,3-oxadiazol-4-yl)-; (1,2,3-oxadiazol-4-yl)-; (3-methyl-1,2,4-oxadiazol-5-yl)-; (5-methyl-1,2,4-oxadiazol-3-yl)-; (4-methyl-3-furazanyl)-; (3-furazanyl)-; (5-methyl-1,2,4-oxadiazol-2-yl)-; (5-methyl-1,2,3-thiadiazol-4-yl)-; (1,2,3-thiadiazol-4-yl)-; (3-methyl-1,2,4-thiadiazol-5-yl)-; (5-methyl-1,2,4-thiadiazol-3-yl)-; (4-methyl-1,2,5-thiadiazol-3-yl)-; (5-methyl-1,3,4-thiadiazol-2-yl)-; (1-methyl-1H-tetrazol-5-yl)-; (1H-tetrazol-5-yl)-; (5-methyl-1H-tetrazol-1-yl)-; (2-methyl-2H-tetrazol-5-yl)-; (2-ethyl-2H-tetrazol-5-yl)-; (5-methyl-2H-tetrazol-2-yl)-; (2H-tetrazol-2-yl)-; (2-pyridyl)-; (6-methyl-2-pyridyl)-; (4-pyridyl)-; (3-pyridyl)-; (6-methyl-3-pyridazinyl)-; (5-methyl-3-pyridazinyl)-; (3-pyridazinyl)-; (4,6-dimethyl-2-pyrimidinyl)-; (4-methyl-2-pyrimidinyl)-; (2-pyrimidinyl)-; (2-methyl-4-pyrimidinyl)-; (2-chloro-4-pyrimidinyl)-; (2,6-dimethyl-4-pyrimidinyl)-; (4-pyrimidinyl)-; (2-methyl-5-pyrimidinyl)-; (6-methyl-2-pyrazinyl)-; (2-pyrazinyl)-; (4,6-dimethyl-1,3,5-triazin-2-yl)-; (4,6-dichloro-1,3,5-triazin-2-yl)-; (1,3,5-triazin-2-yl)-; (4-methyl-1,3,5-triazin-2-yl)-; (3-methyl-1,2,4-triazin-5-yl)-; (3-methyl-1,2,4-triazin-6-yl)-;

and Ar₁₀ may also be, for example, a carbonyl-containing heterocyclic group

wherein each R₂₆ is methyl, each R₂₇ and each R₂₈ are independently hydrogen, C₁-C₃alkyl, C₁-C₃alkoxy, C₁-C₃alkylthio or trifluoromethyl, X₄ is oxygen or sulfur and r=1, 2, 3 or 4.

Where no free valency is indicated in those definitions of Ar₁, Ar₂, Ar₃, Ar₄, Ar₅, Ar₆, Ar₇, Ar₈, A₉, Ar₁₀, Ar₁₁ and Ar₁₂, for example as in

the linkage site is located at the carbon atom labelled “CH” or in a case such as, for example,

at the bonding site indicated at the bottom left.

The alkali metal cation M⁺ (for example in the meaning of O⁻M⁺ in R₃) denotes in the context of the present invention preferably the sodium cation or the potassium cation.

Alkoxy groups preferably have a chain length of from 1 to 6 carbon atoms. Alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy and the isomers of pentyloxy and hexyloxy; preferably methoxy and ethoxy. Alkylcarbonyl is preferably acetyl, propionyl or pivaloyl. Alkoxycarbonyl is, for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl or tert-butoxycarbonyl; preferably methoxycarbonyl or ethoxycarbonyl. Haloalkoxy groups preferably have a chain length of from 1 to 6 carbon atoms. Haloalkoxy is e.g. fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2,2-difluoroethoxy and 2,2,2-trichloroethoxy; preferably difluoromethoxy, 2-chloroethoxy and trifluoromethoxy.

Alkylthio groups preferably have a chain length of from 1 to 8 carbon atoms. Alkylthio is, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio or tert-butylthio, preferably methylthio and ethylthio. Alkylsulfinyl is, for example, methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl, tert-butylsulfinyl; preferably methylsulfinyl and ethylsulfinyl. Alkylsulfonyl is, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl or tert-butylsulfonyl; preferably methylsulfonyl or ethylsulfonyl.

Alkylamino is, for example, methylamino, ethylamino, n-propylamino, isopropylamino or the isomers of butylamine. Dialkylamino is, for example, dimethylamino, methylethylamino, diethylamino, n-propylmethylamino, di-butylamino and di-isopropylamino. Preference is given to alkylamino and dialkylamino groups—including as a component of (N-alkyl)sulfonylamino and N-(alkylamino)sulfonyl groups, such as (N,N-dimethyl)sulfonylamino and N,N-(dimethylamino)sulfonyl—each having a chain length of from 1 to 4 carbon atoms.

Alkoxyalkoxy groups preferably have a chain length of from 1 to 8 carbon atoms. Examples of alkoxyalkoxy are: methoxymethoxy, methoxyethoxy, methoxypropoxy, ethoxymethoxy, ethoxyethoxy, propoxymethoxy and butoxybutoxy. Alkoxyalkyl groups have a chain length of preferably from 1 to 6 carbon atoms. Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxymethyl or isopropoxyethyl.

Alkylthioalkyl groups preferably have from 1 to 8 carbon atoms. Alkylthioalkyl is, for example, methylthiomethyl, methylthioethyl, ethylthiomethyl, ethylthioethyl, n-propylthiomethyl, n-propylthioethyl, isopropylthiomethyl, isopropylthioethyl, butylthiomethyl, butylthioethyl or butylthiobutyl.

The cycloalkyl groups having up to 8 carbon atoms preferably have from 3 to 6 ring carbon atoms, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl. A cycloalkyl group having up to 8 carbon atoms also includes a C₃-C₆alkyl group bonded by way of a methylene or ethylene bridge, for example cyclopropylmethyl, cyclobutylmethyl and cyclopentylmethyl. Cycloalkyl groups, as well as, for example, the oxygen-containing oxiranyl, oxiranylmethyl, 3-oxetanyl, 2- and 3-tetrahydrofuranyl, 2-(2- and 3-tetrahydrofuranyl)methyl, 2-, 3- and 4-tetrahydropyranyl, 2-(2-tetrahydropyranyl)methyl, 1,3-dioxolanyl, 2-(1,3-dioxolanyl)methyl, 4-(1,3-dioxolanyl)methyl, 1,3-dioxanyl, 1,4-dioxanyl and similar saturated groups—especially as a component of Ar₅ in L₁—can also be mono- or poly-substituted by C₁-C₃alkyl, preferably mono- to tetra-substituted by methyl.

Phenyl, including as a component of a substituent such as phenoxy, benzyl, benzyloxy, benzoyl, phenylthio, phenylalkyl, phenoxyalkyl, may be in substituted form. The substituents may in that case be in the ortho-, meta- and/or para-position(s). Preferred substituent positions are the ortho- and para-positions relative to the ring linkage site. The phenyl groups are preferably unsubstituted or mono- or di-substituted, especially unsubstituted or mono-substituted.

Z₁, Z₂ and Z₃ as a C₁-C₆alkyl group which is interrupted by oxygen, —O(CO)—, —(CO)O—, —O(CO)O—, —N(R₁₄)O—, —ONR₁₅—, sulfur, sulfinyl, sulfonyl, —SO₂NR₁₆—, —NR₁₇SO₂— or —NR₁₈— and may be mono- or poly-substituted by a group L₁ when that C₁-C₆alkyl group is interrupted by oxygen, —O(CO)O—, sulfur, sulfinyl or sulfonyl, is to be understood as meaning, for example, a bidentate bridging member —CH₂OCH₂—, —CH₂CH₂OCH₂—, —CH₂OCH₂CH₂—, —CH₂OCH₂CH₂CH₂—, —CH₂OC(O)CH₂—, —CH₂(CO)OCH₂—, —CH₂O(CO)OCH₂—, —CH₂SCH₂—, —CH₂S(O)CH₂—, —CH₂SO₂CH₂—, —CH₂SCH₂CH₂—, —CH₂S(O)CH₂CH₂—, —CH₂SO₂CH₂CH₂—, —CH₂N(CH₃)SO₂CH₂—, —CH₂N(SO₂CH₃)CH₂—, —CH₂N(C(O)CH₃)CH₂—, —CH₂N(COOCH₂CH₃)CH₂— or —CH₂N(COOCH₃)CH₂—, the left-hand bonding site being bonded to the pyridine moiety and the right-hand side to the substituent L₁. And Z₁, Z₂ and Z₃ as a C₂-C₆alkenyl or C₂-C₆alkynyl group which is interrupted by oxygen, —O(CO)—, —(CO)O—, —O(CO)O—, —N(R₁₄)O—, —ONR₁₅—, sulfur, sulfinyl, sulfonyl, —SO₂NR₁₆—, —NR₁₇SO₂— or —NR₁₈— and may be mono- or poly-substituted by a group L₁ is to be understood as meaning, for example, a bidentate bridging member —CH═CHCH₂OCH₂— or —C≡CCH₂OCH₂—. Such an unsubstituted or L₁-substituted C₁-C₆alkyl, C₂-C₆alkenyl or C₂-C₆alkynyl group Z₁, Z₂ or Z₃ which is interrupted by oxygen, —O(CO)—, —(CO)O—, —O(CO)O—, —N(R₁₄)O—, —ONR₁₅—, sulfur, sulfinyl, sulfonyl, —SO₂NR₁₆—, —NR₁₇OS₂— or —NR₁₈— can be either straight-chain or branched, for example as in the case of the bidentate bridging members —CH(CH₃)OCH₂— and —CH₂OCH(CH₃)CH₂—.

The compounds of formula I may occur in various tautomeric forms such as, for example, when R₃ is hydroxy and Q is Q₁, in formulae I′, I″, I′″ and I″″, preference being given to formulae I′ and I″.

Since compounds of formula I may also contain asymmetric carbon atoms, for example in the case of R₁, R₂, A₁, A₂ and Y, their substituents R₆, R₇ and R₈, and also in the case of carbon atoms carrying X₁, X₂, X₃, Z₁, Z₂ and Z₃, and accordingly in any sulfoxides, all the stereoisomers and all chiral <R> and <S> forms are also included. Also included are all constitutional isomeric <E> and <Z> forms in respect of any —C═C— and —C═N— double bonds.

Since R₁ and R₂, like R₇ and R₈ in A₁ and A₂, may each independently of the other have the same or different meanings, the compound of formula I may also occur in various constitutional isomeric forms. The invention therefore relates also to all those constitutional isomeric forms in respect of the spatial arrangement of A₁ and A₂ and the substituents R₁ and R₂ in respect of the substituent R₃ as shown in formulae D₁ to D₄.

The same applies also to the spatial arrangement of the bridging member Y in respect of the carbon atoms carrying R₁ and R₂ when Y is a C₁-C₄alkylene or C₂-C₄alkenylene chain which may be interrupted by oxygen, NR_(5a), sulfur, sulfonyl, sulfinyl, C(O) or C(═NR_(5b)) and/or mono- or poly-substituted by R₆.

The substituent R₃ may also be located on the bridging member, as has already been shown above in formula I″ wherein R₃ is hydroxy. The present invention relates also to those constitutional isomeric forms D₅

of the compounds of formula I.

That arrangement of A₁, A₂, Y and the substituents R₁, R₂, R₄, R₅, R₆, R₇ and R₈ relates accordingly also to all possible tautomeric and stereoisomeric forms of the compounds used as intermediates.

The present invention relates also to the salts which the compounds of formula I are able to form with amines, alkali metal and alkaline earth metal bases or quaternary ammonium bases. Among the alkali metal and alkaline earth metal bases as salt formers, special mention should be made of the hydroxides of lithium, sodium, potassium, magnesium, barium and calcium, but especially the hydroxides of sodium, barium and potassium.

Examples of amines suitable for ammonium salt formation include ammonia as well as primary, secondary and tertiary C₁-C₁₈alkylamines, C₁-C₄hydroxyalkylamines and C₂-C₄-alkoxyalkylamines, for example methylamine, ethylamine, n-propylamine, isopropylamine, the four butylamine isomers, n-amylamine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methylethylamine, methylisopropylamine, methylhexylamine, methylnonylamine, methylpentadecylamine, methyloctadecylamine, ethylbutylamine, ethylheptylamine, ethyloctylamine, hexylheptylamine, hexyloctylamine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-n-amylamine, diisoamylamine, dihexylamine, diheptylamine, dioctylamine, ethanolamine, n-propanolamine, isopropanolamine, N,N-diethanolamine, N-ethylpropanolamine, N-butylethanolamine, allylamine, n-butenyl-2-amine, n-pentenyl-2-amine, 2,3-dimethylbutenyl-2-amine, dibutenyl-2-amine, n-hexenyl-2-amine, propylenediamine, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tri-n-amylamine, methoxyethylamine and ethoxyethylamine; heterocyclic amines, for example pyridine, quinoline, isoquinoline, morpholine, piperidine, pyrrolidine, indoline, quinuclidine and azepine; primary arylamines, for example anilines, methoxyanilines, ethoxyanilines, o-, m- and p-toluidines, phenylenediamines, benzidines, naphthylamines and o-, m- and p-chloroanilines; but especially triethylamine, isopropylamine and diisopropylamine.

Preferred quaternary ammonium bases suitable for salt formation correspond, for example, to the formula [N(R_(a)R_(b)R_(c)R_(d))]OH wherein R_(a), R_(b), R_(c) and R_(d) are each independently of the others C₁-C₄alkyl. Further suitable tetraalkylammonium bases with other anions can be obtained, for example, by anion exchange reactions.

Preference is given to compounds of formula I wherein

-   R₁, R₂, R₆, R₇ and R₈ are each independently of the others hydrogen,     hydroxy, mercapto, NO₂, cyano, halogen, formyl, C₁-C₆alkyl,     C₁-C₆haloalkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-C₆alkynyl,     C₂-C₆haloalkynyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₃-C₆alkenyloxy,     C₃-C₆alkynyloxy, C₃-C₆oxacycloalkyl, C₃-C₆thiacycloalkyl,     C₃-C₆dioxacycloalkyl, C₃-C₆dithiacycloalkyl, C₃-C₆oxathiacycloalkyl,     C₁-C₆alkoxycarbonyl, C₁-C₆alkylcarbonyl, C₁-C₆alkoxycarbonyloxy,     C₁-C₆alkylcarbonyloxy, C₁-C₆alkylthio, C₁-C₆alkylsulfonyl,     C₁-C₆alkylsulfinyl, NR₉R₁₀, C₃-C₆cycloalkyl, tri(C₁-C₆alkyl)silyl,     tri(C₁-C₆alkyl)silyloxy or Ar₁; -   or R₁, R₂, R₆, R₇, R₈ are each independently of the others a     C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl or C₃-C₆cycloalkyl group,     which may be interrupted by oxygen, sulfur, sulfonyl, sulfinyl,     —NR₁₁— or —C(O)— and/or mono-, di- or tri-substituted by hydroxy,     mercapto, NO₂, cyano, halogen, formyl, C₁-C₆alkoxy, C₃-C₆alkenyloxy,     C₃-C₆alkynyloxy, C₁-C₆haloalkoxy, C₁-C₂alkoxy-C₁-C₂alkoxy,     C₁-C₄alkoxycarbonyloxy, C₁-C₄alkylcarbonyloxy, C₁-C₄alkoxycarbonyl,     C₁-C₄alkylcarbonyl, C₁-C₆alkylthio, C₁-C₆alkylsulfinyl,     C₁-C₆alkylsulfonyl, NR₁₂R₁₃, C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl,     C₃-C₆cycloalkyl, tri(C₁-C₆alkyl)silyl, tri(C₁-C₆alkyl)silyloxy or     Ar₂; -   or two substituents R₆ at the same carbon atom together form a     —CH₂O— or a C₂-C₅alkylene chain, which may be interrupted once or     twice by oxygen, sulfur, sulfonyl or sulfinyl and/or mono- or     poly-substituted by R_(6c), with the proviso that two hetero atoms     may not be located next to one another; -   or two substituents R₆ at different carbon atoms together form an     oxygen bridge or a C₁-C₄alkylene chain, which may in turn be     substituted by R_(6c); -   or R₇ and R₈ together form an oxygen bridge, a —CH═CH—CH═CH— bridge     or a C₃-C₄alkylene chain, which may be interrupted by oxygen or     —S(O)_(n1)— and/or mono- or poly-substituted by R_(6d); -   Z₁, Z₂ and Z₃ are each independently of the others     C₁-C₃alkoxy-C₁-C₃alkyl-substituted C₃-C₆cycloalkyl,     tri(C₁-C₆alkyl)silyl, tri(C₁-C₆alkyl)silyloxy or CH═P(phenyl)₃; -   or Z₁, Z₂ and Z₃ are a C₁-C₆alkyl, C₂-C₆alkenyl or C₂-C₆alkynyl     group, which is interrupted by oxygen, —O(CO)—, —(CO)O—, —O(CO)O—,     —N(R₁₄)—O—, —O—NR₁₅—, sulfur, sulfinyl, sulfonyl, —SO₂NR₁₆—,     —NR₁₇SO₂— or —NR₁₈— and is mono- or poly-substituted by L₁; -   L₁ is halogen, hydroxy, amino, formyl, nitro, cyano, mercapto,     carbamoyl, P(O)(OC₁-C₆alkyl)₂, C₁-C₆alkoxy, C₁-C₆haloalkoxy,     C₁-C₆alkoxycarbonyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-C₆alkynyl,     C₂-C₆haloalkynyl, C₃-C₆cycloalkyl, halo-substituted     C₃-C₆-cycloalkyl, C₃-C₆alkenyloxy, C₃-C₆alkynyloxy,     C₃-C₆haloalkenyloxy, cyano-C₁-C₆alkoxy, C₁-C₆alkoxy-C₁-C₆alkoxy,     C₁-C₆alkylthio-C₁-C₆alkoxy, C₁-C₆alkylsulfinyl-C₁-C₆alkoxy,     C₁-C₆alkylsulfonyl-C₁-C₆alkoxy, C₁-C₆alkoxycarbonyl-C₁-C₆alkoxy,     C₁-C₆alkylcarbonyloxy-C₁-C₆alkylcarbonyl, C₁-C₆alkylthio,     C₁-C₆alkylsulfinyl, C₁-C₆alkylsulfonyl, C₁-C₆haloalkylthio,     C₁-C₆haloalkylsulfinyl, C₁-C₆haloalkylsulfonyl or oxiranyl, which     may in turn be substituted by C₁-C₆alkyl, C₁-C₃alkoxy or     C₁-C₃alkoxy-C₁-C₃alkyl, or (3-oxetanyl)-oxy, which may in turn be     substituted by C₁-C₆alkyl, C₁-C₃alkoxy or C₁-C₃alkoxy-C₁-C₃alkyl, or     benzoyloxy, benzyloxy, benzylthio, benzylsulfinyl, benzylsulfonyl,     C₁-C₆alkylamino, di(C₁-C₆alkyl)amino, R₁₉S(O)₂O, R₂₀N(R₂₁)SO₂—,     rhodano, phenyl, phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl     or Ar₄, it being possible for the phenyl-containing groups in turn     to be substituted by one or more C₁-C₃alkyl, C₁-C₃haloalkyl,     C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano, hydroxy or nitro     groups; -   or, when R₁ and R₂ are hydrogen, methyl, halogen or     C₁-C₃alkoxycarbonyl and at the same time Y is other than     C₁-C₂alkylene which may be substituted by hydrogen, halogen or     methyl, or is other than oxygen, sulfur, sulfonyl, sulfinyl, C(O) or     NR_(4a) wherein R_(4a) is hydrogen, C₁-C₄alkyl, formyl or     C₁-C₄alkylcarbonyl, -   L₁ may additionally be hydrogen and Z₁, Z₂ and Z₃ may additionally     be hydrogen, hydroxy, mercapto, NO₂, cyano, halogen, formyl,     C₁-C₆alkyl, C₁-C₆haloalkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl,     C₂-C₆alkynyl, C₂-C₆haloalkynyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy,     C₁-C₆alkoxycarbonyl, C₁-C₆alkylcarbonyl, C₁-C₆alkylthio,     C₁-C₆alkylsulfonyl, C₁-C₆alkylsulfinyl, NR₂₂R₂₃, phenyl which may be     mono- or poly-substituted by C₁-C₃alkyl, C₁-C₃haloalkyl,     C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano, hydroxy or nitro, or     C₃-C₆cycloalkyl, C₃-C₆cycloalkyl substituted by C₁-C₃alkoxy,     C₁-C₃alkoxy-C₁-C₃alkyl or C₁-C₆alkyl, 3-oxetanyl, 3-oxetanyl     substituted by C₁-C₃alkoxy, C₁-C₃alkoxy-C₁-C₃alkyl or C₁-C₆alkyl; or     Ar₅, O—Ar₆, N(R₂₄)Ar₇ or S(O)n₆Ar₈; -   R₉, R₁₁, R₁₃, R₂₃, R₁₆, R₁₇, R₁₈, R₂₀ and R₂₄ are each independently     of the others hydrogen, C₁-C₆alkyl, C₁-C₆haloalkyl,     C₁-C₆alkylcarbonyl, C₁-C₆alkoxycarbonyl, C₁-C₆alkylsulfonyl, phenyl,     it being possible for the phenyl group in turn to be mono- or     poly-substituted by C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy,     C₁-C₆haloalkoxy, halogen, cyano, hydroxy or nitro, or Ar₉; -   R_(6a) and R_(6b) are each independently of the other hydrogen or     C₁-C₆alkyl; or R_(6a) and R_(6b) together are a C₂-C₅alkylene chain; -   R_(6c), R₁₄, R₁₅, R₁₉ and R₂₁ are each independently of the others     C₁-C₆alkyl or C₁-C₆haloalkyl; -   R_(6d), R₁₀, R₁₂ and R₂₂ are each independently of the others     hydrogen or C₁-C₆alkyl; -   Ar₁, Ar₂, Ar₃, Ar₄, Ar₅, Ar₆, Ar₇, A₈ and A₉ are each independently     of the others a five- to ten-membered, monocyclic or fused bicyclic     ring system, which may be aromatic, partially saturated or fully     saturated and may contain from 1 to 4 hetero atoms selected from     nitrogen, oxygen, sulfur, C(O) and C(═NR₂₅), and each ring system     contains not more than two oxygen atoms and not more than two sulfur     atoms, and each ring system may itself be mono- or poly-substituted     by C₁-C₆alkyl, C₁-C₆haloalkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl,     C₂-C₆alkynyl, C₂-C₆haloalkynyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy,     C₃-C₆alkenyloxy, C₃-C₆alkynyloxy, mercapto, amino, hydroxy,     C₁-C₆alkylthio, C₁-C₆haloalkylthio, C₃-C₆alkenylthio,     C₃-C₆-haloalkenylthio, C₃-C₆alkynylthio, C₁-C₃alkoxy-C₁-C₃alkylthio,     C₁-C₄alkylcarbonyl-C₁-C₃alkylthio,     C₁-C₄alkoxycarbonyl-C₁-C₃alkylthio, cyano-C₁-C₃alkylthio,     C₁-C₆alkylsulfinyl, C₁-C₆haloalkylsulfinyl, C₁-C₆alkylsulfonyl,     C₁-C₆haloalkylsulfonyl, aminosulfonyl, C₁-C₂alkylaminosulfonyl,     N,N-di(C₁-C₂alkyl)aminosulfonyl, di(C₁-C₄alkyl)amino, halogen,     cyano, nitro or phenyl, it being possible for the phenyl group in     turn to be substituted by hydroxy, C₁-C₆-alkylthio,     C₁-C₆haloalkylthio, C₃-C₆alkenylthio, C₃-C₆haloalkenylthio,     C₃-C₆alkynylthio, C₁-C₃-alkoxy-C₁-C₃alkylthio,     C₁-C₄alkylcarbonyl-C₁-C₃alkylthio,     C₁-C₄alkoxycarbonyl-C₁-C₃alkylthio, cyano-C₁-C₃alkylthio,     C₁-C₆alkylsulfinyl, C₁-C₆haloalkylsulfinyl, C₁-C₆alkylsulfonyl,     C₁-C₆haloalkylsulfonyl, aminosulfonyl, C₁-C₂alkylaminosulfonyl,     N,N-di(C₁-C₂alkyl)aminosulfonyl, di(C₁-C₄alkyl)amino, halogen, cyano     or nitro, and the substituents at the nitrogen atom in the     heterocyclic ring being other than halogen.

Special mention should be made of compounds of formula I wherein L₁ is hydrogen only when Z₁, Z₂ and Z₃ are a C₁-C₆alkyl group which is interrupted by —O(CO)—, —(CO)O—, —N(R₁₄)O—, —ONR₁₅—, —SO₂NR₁₆—, —NR₁₇SO₂— or —NR₁₈—, or is a C₂-C₆alkenyl or C₂-C₆alkynyl group which is interrupted by oxygen, —O(CO)—, —(CO)O—, —O(CO)O—, —N(R₁₄)O—, —ONR₁₅—, sulfur, sulfinyl, sulfonyl, —SO₂NR₁₆—, —NR₁₇SO₂— or —NR₁₈—; and when, further, either R₁ and R₂ are hydrogen or methyl, or R₁ is halogen or R₂ is C₁-C₃alkoxycarbonyl, and at the same time Y is other than C₁-C₂alkylene which may be substituted by halogen or methyl, or Y is other than oxygen, sulfur, sulfonyl, sulfinyl, C(O) or NR_(4a) wherein R_(4a) is hydrogen, C₁-C₄alkyl, formyl or C₁-C₄alkylcarbonyl.

An outstanding group of compounds of formula I comprises those compounds wherein Z₁, Z₂, Z₃ are C₁-C₃alkylene which is substituted by the following substituents: halogen, hydroxy, amino, formyl, nitro, cyano, mercapto, carbamoyl, P(O)(OC₁-C₆alkyl)₂, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₁-C₆alkoxycarbonyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-C₆alkynyl, C₂-C₆-haloalkynyl, C₃-C₆cycloalkyl, halo-substituted C₃-C₆cycloalkyl, C₃-C₆alkenyloxy, C₃-C₆alkynyloxy, C₃-C₆haloalkenyloxy, cyano-C₁-C₆alkoxy, C₁-C₆alkoxy-C₁-C₆alkoxy, C₁-C₆alkylthio-C₁-C₆alkoxy, C₁-C₆alkylsulfinyl-C₁-C₆alkoxy, C₁-C₆alkylsulfonyl-C₁-C₆alkoxy, C₁-C₆alkoxy-carbonyl-C₁-C₆alkoxy, C₁-C₆alkylcarbonyloxy, C₁-C₆alkylcarbonyl, C₁-C₆alkylthio, C₁-C₆alkylsulfinyl, C₁-C₆alkylsulfonyl, C₁-C₆haloalkylthio, C₁-C₆haloalkylsulfinyl, C₁-C₆haloalkylsulfonyl or oxiranyl, which may in turn be substituted by C₁-C₃alkyl, C₁-C₃alkoxy or C₁-C₃alkoxy-C₁-C₃alkyl, or (3-oxetanyl)-oxy, which may in turn be substituted by C₁-C₆alkyl, C₁-C₃alkoxy or C₁-C₃alkoxy-C₁-C₃alkyl, or benzoyloxy, benzyloxy, benzylthio, benzylsulfinyl, benzylsulfonyl, C₁-C₆alkylamino, di(C₁-C₆alkyl)amino, R₁₉S(O)₂O, R₂₀N(R₂₁)SO₂—, rhodano, phenyl, phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl or Ar₄, it being possible for the phenyl-containing groups in turn to be substituted by one or more C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃-alkoxy, C₁-C₃haloalkoxy, halogen, cyano, hydroxy or nitro groups;

-   or, when R₁ and R₂ are hydrogen, methyl, halogen or     C₁-C₃alkoxycarbonyl and at the same time Y is other than     C₁-C₂alkylene which may be substituted by halogen or methyl, or is     other than oxygen, sulfur, sulfonyl, sulfinyl, C(O) or NR_(4a)     wherein R_(4a) is hydrogen, C₁-C₄-alkyl, formyl or     C₁-C₄alkylcarbonyl, -   L₁ may additionally be hydrogen and Z₁, Z₂ and Z₃ may additionally     be hydrogen, hydroxy, mercapto, NO₂, cyano, halogen, formyl,     C₁-C₆alkyl, C₁-C₆haloalkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl,     C₂-C₆alkynyl, C₂-C₆haloalkynyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy,     C₁-C₆alkoxycarbonyl, C₁-C₆alkylcarbonyl, C₁-C₆alkylthio,     C₁-C₆alkylsulfonyl, C₁-C₆alkylsulfinyl, NR₂₂R₂₃, phenyl which may be     mono- or poly-substituted by C₁-C₃alkyl, C₁-C₃haloalkyl,     C₁-C₃alkoxy, C₁-C₃-haloalkoxy, halogen, cyano, hydroxy or nitro, or     C₃-C₆cycloalkyl, C₃-C₆cycloalkyl substituted by C₁-C₃alkoxy,     C₁-C₃alkoxy-C₁-C₃alkyl or C₁-C₃alkyl, 3-oxetanyl, 3-oxetanyl     substituted by C₁-C₃alkoxy, C₁-C₃alkoxy-C₁-C₃alkyl or C₁-C₆alkyl, or     Ar₅, O—Ar₆, N(R₂₄)Ar₇ or S(O)n₆Ar₈.

Preferred compounds of formula I are those wherein p is 0. Preferably at least one group Z₁, Z₂ or Z₃ is in the ortho-position relative to the carbonyl group; in preferred compounds, in addition, m₁, m₂ and m₃ are the number 1. Also preferred are compounds of formula I wherein Q is a group Q₁ or Q₂, especially the group Q₁.

Also preferred are those compounds of formula I wherein Y is oxygen, NCO₂methyl, NSO₂CH₃, NC(O)CH₃, sulfur, sulfinyl, sulfonyl, C(O) or a C₁-C₂alkylene chain. Outstanding compounds are those wherein Y is a C₁-C₂alkylene chain or oxygen, and wherein A₁ is CR₇, A₂ is CR₈ and R₁, R₂, R₆, R₇, R₈ are each independently of the others hydrogen or methyl, especially Y is methylene or ethylene and R₁, R₂, R₆, R₇, R₈ are each hydrogen.

Especially interesting compounds of formula I are those wherein Z₁ is C₁-C₃alkylene which may be interrupted by oxygen, especially a bidentate group of form —CH₂—, —CH₂CH₂—, —OCH₂—, —OCH₂CH₂—, —CH₂O—, —CH₂CH₂O—, —CH₂OCH₂— or —CH₂CH₂CH₂O—, and L₁ is preferably hydrogen, halogen, cyano, C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-C₆alkynyl, C₂-C₆haloalkynyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₁-C₆alkoxy-C₁-C₆alkoxy. Especially preferred are compounds of formula I wherein Z₁ or Z₁-L₁ is CH₃, CH₂CH₃, CH₂CH₂CH₃, CHC(CH₃)₂, CH₂OCH₂CH₂OCH₃, CH₂OCH₂CH₂OCH₂CH₃, CH₂OCH₃, CH₂OCH₂CH₃, CH₂OCH(CH₃)₂, CH₂OCH₂CF₃, CH₂OCH₂CH═CH₂, CH₂OCH₂CCH, CH₂OCH₂CCCH₃, CH₂OCH₂CH₂CCH, CH₂OCH₂CN, CH₂OCH₂C₂CN, CH₂OCH₂CH₂CH₂OCH₃, CH₂OCH₂CH₂OCH₂CH₂OCH₃, CH₂OCH₂CH₂CH₂OCF₃, CH₂CH₂OCH₃, CH₂CH₂OCH₂CH₃, CH₂CH₂CH₂OCH₃, CH₂CH₂CH₂OCH₂CH₃ or CH₂CH₂OCH₂CH₂OCH₃, more especially CH₃, CH₂CH₂CH₂OCH₃ or CH₂OCH₂CH₂OCH₃, especially prominent compounds being those wherein Y is methylene, ethylene or oxygen, A₁ is CR₇, A₂ is CR₈ and R₁, R₂, R₆, R₇, R₈ are each independently of the others hydrogen or methyl. Of that group, preference is given to those compounds wherein Q is Q₁, p₁ is 0 and m₁ is 1, the group (Z₁)m₁ is in the ortho-position relative to the carbonyl group, and R₃ is hydroxy.

Special emphasis should also be given to compounds of formula I wherein Q is Q₁, Z₁ is C₁-C₃alkylene which may be interrupted by oxygen, Z₁ being especially a bidentate group of form —CH₂—, —CH₂CH₂—, —OCH₂—, —OCH₂CH₂—, —CH₂O—, —CH₂CH₂O—, —CH₂OCH₂— or —CH₂CH₂CH₂O—, and L₁ is preferably a monocyclic group

wherein R₂₆ is hydrogen or methyl, R₂₇ is hydrogen, C₁-C₃alkyl, C₁-C₃alkoxy, C₁-C₃alkylthio or trifluoromethyl and X₄ is oxygen or sulfur.

Where no free valency is indicated in those preferred definitions of L₁, for example as in

the linkage site is located at the carbon atom labelled “CH” or in the case of

at the carbon atom labelled “CH₂” or in a case such as, for example,

at the bonding site indicated at the bottom left.

In a further preferred group of compounds of formula I, X₁, X₂ and X₃ are C₁-C₃haloalkyl, especially CF₃, CF₂CF₃, CF₂Cl or CF₂H, more especially CF₃ or CF₂H.

An especially preferred group of compounds of formula I comprises those compounds wherein

-   Y is oxygen, C(═CR_(6a)R_(6b)) or a C₁-C₄alkylene chain which may be     mono- or poly-substituted by R₆; -   A₁ is CR₇; -   A₂ is CR₈; -   R₁, R₂, R₆, R_(6a), R_(6b), R₇ and R₈ are each independently of the     others hydrogen, C₁-C₆alkyl or C₁-C₆alkoxycarbonyl; -   or two substituents R₆ at the same carbon atom together form a     C₂-C₅alkylene chain; -   R₃ is hydroxy; -   Q is the radical Q₁; -   p₁ is 0; -   m₁ is 1; -   X₁ is C₁-C₆haloalkyl; -   Z₁ is a C₁-C₆alkyl group which is interrupted by oxygen and is mono-     or poly-substituted by L₁; it also being possible for L₁ to be     bonded at the terminal carbon atom of the C₁-C₆alkyl group; -   or Z₁ is C₁-C₆alkyl; -   and L₁ is C₁-C₆alkoxy; -   and agronomically acceptable salts/isomers/enantiomers/tautomers of     those compounds.

The compounds of formula I can be prepared by means of processes known per se, e.g. as described in WO/0039094, as indicated below with reference to the examples of compounds of formula Ia

wherein R₁, R₂, A₁, A₂, Y, X₁, Z₁, m₁ and p₁ are as defined above.

In a preferred process, for example in the case of compounds of formula Ia

wherein R₁, R₂, A₁, A₂ and Y are as defined above and Q is a group Q₁,

-   a) a compound of formula Q₁a     wherein Z₁, m₁, X₁ and p₁ are as defined above and E₁ is a leaving     group, for example halogen or cyano, is reacted in an inert organic     solvent, in the presence of a base, with a compound of formula Da     wherein Y, R₁, R₂, A₂ and A₁ are as defined for formula I, to form     compound(s) of formula IIa and/or IIb     and the latter is(are) then isomerised, for example in the presence     of a base and a catalytic amount of an acylating agent, for example     dimethylaminopyridine (DMAP), or a cyanide source, e.g. acetone     cyanohydrin, potassium cyanide or trimethylsilyl cyanide; or -   b) a compound of formula Q₁b     wherein Z₁, m₁, p₁ and X₁ are as defined for formula I, is reacted     with a compound of formula Da     wherein Y, R₁, R₂, A₁ and A₂ are as defined for formula I, in an     inert organic solvent, in the presence of a base and a coupling     reagent, to form compound(s) of formula IIa and/or IIb     and the latter is(are) then isomerised, for example as described     under Route a).

The intermediates of formulae Da, IIa and IIb are novel and have been developed especially for the preparation of the compounds of formula I. The present invention therefore relates also thereto. The novel intermediates of formulae Da, IIa, IIb correspond, in summary, to the general formulae IIIa and IIIb

wherein R₁, R₂, Y, A₁ and A₂ are as defined above and R₂₉ is OH or OC(O)Q wherein Q is as defined for formula I.

The preparation of the compounds of formula I is illustrated in greater detail in the following Reaction Schemes.

According to Reaction Scheme 1 it is preferable to prepare the compounds of formula I having the group Q₁, Q₂ and Q₃ wherein R₃ is hydroxy and p₁, p₂ and p₃ are 0.

Compounds of formula I wherein p₁, p₂ and p₃ are 1, that is to say the corresponding N-oxides of formula I, can be prepared by reacting a compound of formula I wherein p₁, p₂ and p₃ are 0 with a suitable oxidising agent, for example with the H₂O₂-urea adduct in the presence of an acid anhydride, e.g. trifluoroacetic anhydride. Such oxidations are known in the literature, for example from J. Med. Chem., 32 (12), 2561-73, 1989 or WO 00/15615.

For the preparation of the compounds of formula I wherein Q is the groups Q₁, Q₂ and Q₃ and R₃ is hydroxy, for example in accordance with Reaction Scheme 1, Route a), the carboxylic acid derivatives of formula Q₁a wherein E₁ is a leaving group, e.g. halogen, for example iodine, bromine and especially chlorine, N-oxyphthalimide or N,O-dimethylhydroxylamino, or part of an activated ester, e.g.

(formed from dicyclohexylcarbodiimide (DCC) and the corresponding carboxylic acid) or

(formed from N-ethyl-N′-(3-dimethylaminopropyl)-carbodiimide (EDC) and the corresponding carboxylic acid) are used as starting materials. They are reacted in an inert, organic solvent, e.g. a halogenated hydrocarbon, for example dichloromethane, a nitrile, for example acetonitrile, or an aromatic hydrocarbon, for example toluene, and in the presence of a base, e.g. an alkylamine, for example triethylamine, an aromatic amine, for example pyridine or 4-dimethylaminopyridine (DMAP), with the dione derivatives of formula Da to form the isomeric enol esters of formula IIa or IIb. That esterification can be carried out at temperatures of from 0° C. to 110° C.

The isomerisation of the enol ester derivatives of formulae IIa and IIb to form the derivatives of formula I wherein R₃ is hydroxy can be carried out, for example, analogously to EP-A-0 353 187, EP-A-0 316 491 or WO 97/46530 in the presence of a base. e.g. an alkylamine, for example triethylamine, a carbonate, for example potassium carbonate, and a catalytic amount of DMAP or a catalytic amount of a cyanide source, for example acetone cyano-hydrin, potassium cyanide or trimethylsilyl cyanide. The two reaction steps can be carried out in situ, especially when a cyanide compound of formula Q₁a (E₁=cyano) is used, or in the presence of a catalytic amount of acetone cyanohydrin or potassium cyanide, without isolation of the intermediates IIa and IIb.

According to Reaction Scheme 1, Route b), the desired derivatives of formula I wherein R₃ is hydroxy can be obtained e.g. analogously to E. Haslem, Tetrahedron, 2409-2433, 36, 1980 by first preparing enol esters of formula IIa and/or IIb by means of esterification of the carboxylic acids of formula Q₁b with the dione derivatives of formula Da in an inert solvent, for example a halogenated hydrocarbon, for example dichloromethane, a nitrile, for example acetonitrile, or an aromatic hydrocarbon, for example toluene, in the presence of a base, e.g. an alkylamine, for example triethylamine, and a coupling agent, for example 2-chloro-1-methyl-pyridinium iodide, which enol esters are then converted in situ or in a second step into the compounds of formula I. That reaction takes place, depending upon the solvent used, at temperatures of from 0° C. to 110° C. and yields first, as described under Route a), the isomeric esters of formulae IIa and IIb, which can be isomerised to the desired derivatives of formula I (R₃=hydroxy) as described under Route a), for example in the presence of a base and a catalytic amount of DMAP, or a cyanide source, e.g. acetone cyanohydrin.

The activated carboxylic acid derivatives of formula Q₁a in Reaction Scheme 1 (Route a) wherein E₁ is a leaving group, e.g. halogen, for example bromine, iodine or especially chlorine, can be prepared according to known standard methods, as described e.g. in C. Ferri “Reaktionen der organischen Synthese”, Georg Thieme Verlag, Stuttgart, 1978, page 460 ff. Such reactions are generally known and various variations in respect of the leaving group E₁ are described in the literature.

Compounds of formula I wherein R₃ is other than hydroxy or halogen can be prepared in accordance with conversion reactions generally known from the literature by nucleophilic substitution reactions on chlorides of formula I wherein R₃ is chlorine, which are readily obtainable from compounds of formula I wherein R₃ is hydroxy, likewise in accordance with known processes, by reaction with a chlorinating agent, such as phosgene, thionyl chloride or oxalyl chloride. In such a reaction there are used, for example, mercaptans, thiophenols or heterocyclic thiols in the presence of a base, for example 5-ethyl-2-methylpyridine, diisopropyl-ethylamine, triethylamine, sodium hydrogen carbonate, sodium acetate or potassium carbonate.

Compounds of formula I wherein the substituent R₃ contains thio groups can be oxidised to the corresponding sulfones and sulfoxides of formula I analogously to known standard methods, e.g. with peracids, for example meta-chloroperbenzoic acid (m-CPBA) or peracetic acid. In that reaction the degree of oxidation at the sulfur atom (SO— or SO₂—) can be controlled by the amount of oxidising agent. Other sulfur-containing groups, for example those in the meanings of R₁, R₂, R₆, R₇, R₈, L₁, X₁, X₂, X₃ or Y, or in alkyl groups and chains interrupted by sulfur, as may occur, for example, in Z₁, Z₂ and Z₃, can be oxidised with a suitable oxidising agent, such as m-CPBA or sodium periodate, to the corresponding sulfone and sulfine (sulfoxido) groups directly in compounds of formula I, as well as in intermediates of formulae IIa, IIb, Da and Db (hereinbelow).

The derivatives of formula I so obtained wherein R₃ is other than hydroxy can also be in various isomeric forms, which can optionally be isolated in pure form. The invention therefore includes all those stereoisomeric forms. Examples of those isomeric forms are the following formulae I′, I″ and I″′, as shown with reference to compounds of formula I wherein Q is group Q₁.

The compounds of formula Da used as starting materials can be prepared, for example, by treating a compound of formula Db

wherein A₁, A₂, R₁, R₂ and Y are as defined for formula I, Xa is chlorine or bromine and R₃ is hydroxy or C₁-C₆alkoxy, in the presence of a suitable reducing agent, e.g. tributyltin hydride, or zinc in acetic acid, optionally followed, when R₃ is C₁-C₆alkoxy, by aftertreatment in the presence of a hydrolysing agent, e.g. dilute hydrochloric acid or aqueous p-toluenesulfonic acid.

Specifically the compounds of formula Db above wherein R₁ and R₂ are each hydrogen or methyl, A₁ and A₂ are each methylene, Y is oxygen, methylene or ethylene, R₃ is chlorine, bromine or hydroxy and Xa is chlorine or bromine are known from Organic Letters 2002, 4, 1997; Archiv der Pharmazie 1987, 320, 1138; J. Amer. Chem. Soc. 1968, 90 2376 and from U.S. Pat. No. 3,538,117 and can be prepared in accordance with the methods described therein.

The compounds of formula Da used as starting materials can accordingly also be prepared very generally in accordance with those known methods, by reacting a dienophilic compound of formula IV

wherein A₁, A₂, R₁, R₂ and Y are as defined above, in an inert solvent, such as dichloromethane, 1,2-dichloroethane, toluene or chlorobenzene, optionally at elevated temperature or under elevated pressure, in a reaction similar to a Diels-Alder reaction, with a tetrahalocyclopropene of formula V

wherein Xa is chlorine or bromine, and then hydrolysing the resulting bicyclic compound of formula VI

wherein A₁, A₂, R₁, R₂, Xa and Y are as defined above, optionally in the presence of a suitable catalyst, for example silver nitrate or the silver tetrafluoroborate salt, or an acid, such as 90-98% sulfuric acid, 90% trifluoroacetic acid or p-toluenesulfonic acid, or reacting it with an alcoholate, for example sodium methanolate, potassium ethanolate or lithium isopropanolate, in order thus to obtain a compound of formula Db

wherein A₁, A₂, R₁, R₂, Xa and Y are as defined above, and R₃ depending upon the reaction conditions is either hydroxy, C₁-C₆alkoxy, chlorine or bromine, which is then further reduced and/or hydrolysed to form a novel compound of formula Da

wherein A₁, A₂, R₁, R₂ and Y are as defined above.

Compounds of formula VI can thus be reacted further, for example in the presence of 90-98% sulfuric acid at elevated temperature of about 80-100° C., to form compounds of formula Db wherein R₃ is hydroxy and Xa is chlorine or bromine, as described in greater detail in J. Amer. Chem. Soc. 1968, 90, 2376.

It is also possible for compounds of formula VI to be converted into compounds of formula Db wherein R₃ and Xa are both chlorine or bromine, for example in the presence of 90% trifluoroacetic acid at boiling temperature or in the presence of aqueous silver nitrate at ambient temperature, as described in Archiv der Pharmazie 1987, 320, 1138 and in Organic Letters 2002, 4, 1997.

On the other hand, compounds of formula VI can be converted into compounds of formula Db wherein R₃ is C₁-C₆alkoxy and Xa is chlorine or bromine in good yields at ambient temperature in the presence of alcoholates of formula R_(3a)O⁻M⁺ wherein R_(3a) is accordingly C₁-C₆alkyl and M⁺ is an alkali metal salt, in a solvent, such as an alcohol R_(3a)OH, toluene or ether, e.g. tetrahydrofuran, dimethoxyethane.

It is also possible for compounds of formula Db wherein Xa is chlorine or bromine and R₃ is hydroxy or C₁-C₆alkoxy to be reduced in the presence of reducing agents, e.g. tributyltin hydride, in an organic solvent, such as toluene or tetrahydrofuran, to form compounds of formula Db wherein Xa is hydrogen, as is well known according to general methods from the literature for the reduction of a halogen in a position adjacent to a carbonyl group (see e.g. Comprehensive Org. Funct. Group, Transformations, Vol. 1. ed. S. M. Roberts, Pergamon Press Oxford, 1995, pages 1-11).

Finally, compounds of formula Db wherein R₃ is C₁-C₆alkoxy, chlorine or bromine and Xa is hydrogen can be hydrolysed to compounds of formula Da in the presence of acids, e.g. dilute hydrochloric acid, dilute sulfuric acid or p-toluenesulfonic acid.

The general reaction sequences for the preparation of compounds of formulae Da and Db from compounds of formulae IV and V via intermediates of formula VI are shown in the following Scheme.

In the reaction of compounds of formula VI and/or Db wherein A₁, A₂, R₁, R₂, Xa and Y are as defined above and R₃ is C₁-C₆alkoxy with alcoholates of formula R_(3a)O⁻M⁺, it is also possible for compounds of formula VII to be formed

wherein A₁, A₂, R₁, R₂, Xa and Y are as defined above and R_(3a) is C₁-C₆alkyl or, when glycol is used, two R_(3a) together are —CH₂CH₂—. Those compounds too can be reacted under the reduction conditions mentioned above, for example with tributyltin hydride or with zinc in the presence of acetic acid, by way of a compound of formula VIIa

wherein A₁, A₂, R₁, R₂, R_(3a) and Y are as defined above, and subsequent hydrolysis, for example with dilute hydrochloric acid or a catalytic amount of p-toluenesulfonic acid in water, to form the compounds of formulae Da and Db

wherein A₁, A₂, R₁, R₂ and Y are as defined above and R₃ is hydroxy and Xa is hydrogen, as is shown generally in the following Scheme.

In a further process, compounds of formula Da can also be prepared either by conversion of a compound of formula VIII

wherein R₁, R₂, A₁, A₂, Y are as defined above and Ra is C₁-C₆alkyl or, when glycol is used, two R_(3a) together are —CH₂CH₂—, by hydrolysis, e.g. by treatment with an aqueous acid, Route c), or by conversion of a compound of formula IX

wherein R₁, R₂, A₁, A₂, Y are as defined above, by means of oxidation, e.g. with selenium dioxide, Route d), first into a diketo compound of formula X

wherein R₁, R₂, A₁, A₂, Y are as defined above, and subsequent conversion of that compound by carbene insertion, e.g. with diazomethane or with trimethylsilyl-diazomethane, into the 1,3-dione compound Da.

Those processes are also known per se to the person skilled in the art; the compounds can be prepared, depending upon the functionality of the groups R₁, R₂, A₁, A₂ and Y, by general reaction routes shown in the following Scheme:

Using such routes it is readily possible to obtain, in particular, those compounds of formula VIII wherein Y is a C₂alkylene chain substituted by R₆, wherein R₆ is for example alkoxy, benzyloxy, alkylcarbonyl, alkoxycarbonyl, alkylthio or alkylsulfonyl.

Methods of obtaining the starting compounds of formula VII used in the above-mentioned process are known, for example, from Acc. Chem. Res. 2002, 856; J.O.C. 2002, 67, 6493; Organic Letters 2002, 2477; Synlett, 2002,1520; Chem. Commun. 2001, 1624; Synlett, 2000, 421; Tetrahedron Letters, 1999, 8431; J.O.C. 1999, 64, 4102; J.A.C.S. 1998, 129, 13254; Tetrahedron Letters, 1998, 659; Synlett, 1997, 1351. Methods of obtaining the starting compounds of formula IX are described, for example, in Org. Lettr. 2002, 2063; Synthetic Commun. 2001, 707; J.A.C.S. 2001, 123, 1569; Synlett, 1999, 225; Synlett, 1997, 786; Tetrahedron Letters, 1996, 7295; Synthesis, 1995, 845. Compounds of formula X are known, for example, from Synthesis, 2000, 850.

The transformations according to Route d) are likewise known, for example from Tetr. 1986, 42, 3491. Oxidation is preferably carried out with selenium dioxide in a solvent, such as acetic acid, at temperatures of from about 20° C. to about 120° C. and the carbene insertion with diazomethane is preferably effected at from about −40° C. to about 50° C. in a solvent, such as dichloromethane or diethyl ether. The carbene insertion can also be carried out with trimethylsilyldiazomethane, it having proved advantageous to work in the presence of a Lewis acid catalyst, such as boron trifluoride etherate, for example at temperatures of from about −15° C. to about +25° C.

In principle, however, the compounds of formulae Da, Db, VII, VIIa, VIII, IX and X used as starting materials and as intermediates can be prepared, in dependence upon the substituent pattern A₁, A₂, R₁, R₂ and Y and also in dependence upon the availability of the starting materials, according to any desired methods and reaction routes, there being no limitation in respect of the process variants indicated above.

The compounds of formula Da wherein R₁, R₂, A₁, A₂ and Y are as defined above, and also compounds of formula Db wherein R₁, R₂, A₁, A₂ and Y are as defined above and R₃ is chlorine, bromine, hydroxy or C₁-C₆alkoxy and Xa is hydrogen, chlorine or bromine, with the exception of the compounds 3-chloro-8-oxa-bicyclo[3.2.1]oct-6-ene-2,4-dione; 3-chloro-bicyclo[3.2.1]oct-6-ene-2,4-dione; 3-chloro-4-hydroxy-bicyclo[3.2.1]octa-3,6-dien-2-one; 3,4-dibromo-8-oxa-bicyclo[3.2.1]octa-3,6-dien-2-one; 3,4-dibromo-1,5-dimethyl-8-oxa-bicyclo-[3.2.1]octa-3,6-dien-2-one; 3,4-dibromo-bicyclo[3.2.1]octa-3,6-dien-2-one; 3,4-dichloro-8-oxa-bicyclo[3.2.1]octa-3,6-dien-2-one; 3,4-dichloro-bicyclo[3.2.1]octa-3,6-dien-2-one and 7,8-dibromo-5,9-dihydro-5,9-methano-benzocyclohepten-6-one, and also the compounds of formula VII are novel and constitute valuable intermediates for the preparation of compounds of formula I. The present invention accordingly relates likewise thereto.

The compounds of formulae Q_(1a), Q_(2a) and Q_(3a) used as starting materials and their corresponding acids Q_(1b), Q_(2b) and Q_(3b) are known from the publications WO 00/15615 and WO 01/94339 or can be prepared in accordance with the methods described therein.

The compounds of formula V used as starting material are likewise known, for example from Synthesis 1987, 260 and from J. Amer. Chem. Soc. 1968, 90 2376.

A large number of known standard methods are available for the preparation of all further compounds of formula I functionalised in accordance with the definition of A₁, A₂, R₁, R₂, Y and Q, for example alkylation, halogenation, acylation, amidation, oximation, oxidation and reduction, the choice of a suitable preparation process being governed by the properties (reactivities) of the substituents in question in the respective intermediates of formulae I, Da, Db, VI, VII and VIIa, and especially the starting materials of formulae IV and V and Q_(1b), Q_(2b) and Q_(3b).

The reactions to form compounds of formula I are advantageously carried out in aprotic, inert organic solvents. Such solvents are hydrocarbons, such as benzene, toluene, xylene or cyclohexane, chlorinated hydrocarbons, such as dichloromethane, trichloromethane, tetrachloromethane or chlorobenzene, ethers, such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran or dioxane, nitriles, such as acetonitrile or propionitrile, amides, such as N,N-dimethylformamide, diethylformamide or N-methylpyrrolidinone. The reaction temperatures are preferably from −20° C. to +120° C. The reactions generally proceed slightly exothermically and can generally be carried out at room temperature. In order to shorten the reaction time or to initiate the reaction, brief heating, up to the boiling point of the reaction mixture, can be carried out. The reaction times can likewise be shortened by the addition of a few drops of base as reaction catalyst. Suitable bases are especially tertiary amines, such as trimethylamine, triethylamine, quinuclidine, 1,4-diazabicyclo[2.2.2]octane, 1,5-diazabicyclo[4.3.0]non-5-ene or 1,5-diazabicyclo[5.4.0]undec-7-ene. It is also possible, however, to use as bases inorganic bases, such as hydrides, e.g. sodium or calcium hydride, hydroxides, e.g. sodium or potassium hydroxide, carbonates, e.g. sodium or potassium carbonate, or hydrogen carbonates, e.g. potassium or sodium hydrogen carbonate. The bases can be used as such or alternatively with catalytic amounts of a phase transfer catalyst, e.g. crown ethers, especially 18-crown-6, or tetraalkylammonium salts.

The end products of formula I can be isolated in conventional manner by concentration or evaporation of the solvent and purified by recrystallisation or trituration of the solid residue in solvents in which they are not readily soluble, such as ethers, aromatic hydrocarbons or chlorinated hydrocarbons, by distillation or by means of column chromatography or by means of the HPLC technique using a suitable eluant.

The sequence in which the reactions should be carried out in order as far as possible to avoid secondary reactions will be familiar to the person skilled in the art. Unless the synthesis is specifically aimed at the isolation of pure isomers, the product may be obtained in the form of a mixture of two or more isomers, for example chiral centres in the case of alkyl groups or cis/trans isomerism in the case of alkenyl groups or <E> or <Z> forms. All such isomers can be separated by methods known per se, for example chromatography, crystallisation, or produced in the desired form by means of a specific reaction procedure.

For the use according to the invention of the compounds of formula I, or of compositions comprising them, there come into consideration all methods of application customary in agriculture, for example pre-emergence application, post-emergence application and seed dressing, and also various methods and techniques such as, for example, the controlled release of active ingredient. For that purpose a solution of the active ingredient is applied to mineral granule carriers or polymerised granules (urea/formaldehyde) and dried. If required, it is additionally possible to apply a coating (coated granules), which allows the active ingredient to be released in metered amounts over a specific period of time.

The invention therefore relates also to a herbicidal and plant-growth-inhibiting composition comprising a herbicidally effective amount of a compound of formula I according to claim 1 on an inert carrier.

The compounds of formula I can be used as herbicides in unmodified form, that is to say as obtained in the synthesis, but they are preferably formulated in customary manner together with the adjuvants conventionally employed in formulation technology e.g. into emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, suspensions, mixtures of a suspension and an emulsion (suspoemulsions), wettable powders, soluble powders, dusts, granules or microcapsules. Such formulations are described, for example, on pages 9 to 13 of WO 97/34485. As with the nature of the compositions, the methods of application, such as spraying, atomising, dusting, wetting, scattering or pouring, are selected in accordance with the intended objectives and the prevailing circumstances.

The formulations, that is to say the compositions, preparations or mixtures comprising the compound (active ingredient) of formula I or at least one compound of formula I and, usually, one or more solid or liquid formulation adjuvants, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with the formulation adjuvants, for example solvents or solid carriers. Surface-active compounds (surfactants) may also be used in addition in the preparation of the formulations. Examples of solvents and solid carriers are given, for example, on page 6 of WO 97/34485.

Depending upon the nature of the compound of formula I to be formulated, suitable surface-active compounds are non-ionic, cationic and/or anionic surfactants and surfactant mixtures having good emulsifying, dispersing and wetting properties.

Examples of suitable anionic, non-ionic and cationic surfactants are listed, for example, on pages 7 and 8 of WO 97/34485.

In addition, the surfactants conventionally employed in formulation technology, which are described, inter alia, in “McCutcheon's Detergents and Emulsifiers Annual” MC Publishing Corp., Ridgewood N.J., 1981, Stache, H., “Tensid-Taschenbuch”, Carl Hanser Verlag, Munich/Vienna 1981, and M. and J. Ash, “Encyclopedia of Surfactants”, Vol. I-III, Chemical Publishing Co., New York, 1980-81, are also suitable for the preparation of the herbicidal compositions according to the invention.

The compositions according to the invention can additionally include an additive comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters thereof or mixtures of such oils and oil derivatives.

The amount of oil additive in the composition according to the invention is generally from 0.01 to 2%, based on the spray mixture. For example, the oil additive can be added to the spray tank in the desired concentration after the spray mixture has been prepared.

Preferred oil additives comprise mineral oils or an oil of vegetable origin, for example rapeseed oil, olive oil or sunflower oil, emulsified vegetable oil, such as AMIGO® obtainable from Rhône-Poulenc Canada Inc., alkyl esters of oils of vegetable origin, for example the methyl derivatives, or an oil of animal origin, such as fish oil or beef tallow. A preferred additive contains as active components essentially 80% by weight alkyl esters of fish oils and 15% by weight methylated rapeseed oil, and also 5% by weight of customary emulsifiers and pH modifiers.

Especially preferred oil additives comprise alkyl esters of higher fatty acids (C₈-C₂₂), especially the methyl derivatives of C₁₂-C₁₈ fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid. Those esters are known as methyl laurate (CAS-111-82-0), methyl palmitate (CAS-112-39-0) and methyl oleate (CAS-112-62-9). A preferred fatty acid methyl ester derivative is Emery® 2230 and 2231 (Henkel subsidiary Cognis GMBH, DE).

The application and action of the oil additives can be improved by combining them with surface-active substances, such as non-ionic, anionic or cationic surfactants. Examples of suitable anionic, non-ionic and cationic surfactants are listed on pages 7 and 8 of WO 97/34485.

Preferred surface-active substances are anionic surfactants of the dodecylbenzylsulfonate type, especially the calcium salts thereof, and also non-ionic surfactants of the fatty alcohol ethoxylate type. Special preference is given to ethoxylated C₁₂-C₂₂ fatty alcohols having a degree of ethoxylation of from 5 to 40. Examples of commercially available, preferred surfactants are the Genapol types (Clariant AG, Muttenz, Switzerland). Also preferred for use as surface-active substances are silicone surfactants, especially polyalkyl-oxide-modified heptamethyltrisiloxanes, such as are commercially available as e.g. Silwet L-77®, and also perfluorinated surfactants. The concentration of surface-active substances in relation to the total additive is generally from 1 to 30% by weight.

Examples of oil additives that consist of mixtures of oils or mineral oils or derivatives thereof with surfactants are Edenor ME SU®, Turbocharge® (Zeneca Agro, Stoney Creek, Ontario, Calif.) and Actipron® (BP Oil UK Limited, GB).

The addition of an organic solvent to the oil additive/surfactant mixture can also bring about a further enhancement of action. Suitable solvents are, for example, Solvesso® (ESSO) and Aromatic Solvent® (Exxon Corporation) types.

The concentration of such solvents can be from 10 to 80% by weight of the total weight.

Such oil additives, which are also described, for example, in U.S. Pat. No. 4,834,908, are suitable for the composition according to the invention. A commercially available oil additive is known by the name MERGE®, is obtainable from the BASF Corporation and is essentially described, for example, in U.S. Pat. No. 4,834,908 in col. 5, as Example COC-1. A further oil additive that is preferred according to the invention is SCORE® (Novartis Crop Protection Canada.)

In addition to the oil additives listed above, in order to enhance the action of the compositions according to the invention it is also possible for formulations of alkyl pyrrolidones, such as are commercially available e.g. as Agrimax®, to be added to the spray mixture. Formulations of synthetic latices, such as, for example, polyacrylamide, polyvinyl compounds or poly-1-p-menthene, such as are commercially available as e.g. Bond®, Courier® or Emerald®, can also be used to enhance action. Solutions that contain propionic acid, for example Eurogkem Pen-e-trate®, can also be added as action-enhancing agent to the spray mixture.

The herbicidal formulations generally contain from 0.1 to 99% by weight, especially from 0.1 to 95% by weight, of herbicide, from 1 to 99.9% by weight, especially from 5 to 99.8% by weight, of a solid or liquid formulation adjuvant, and from 0 to 25% by weight, especially from 0.1 to 25% by weight, of a surfactant. Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations. The compositions may also comprise further ingredients, such as stabilisers, for example vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rapeseed oil or soybean oil), anti-foams, for example silicone oil, preservatives, viscosity regulators, binders, tackifiers, and also fertilisers or other active ingredients.

The compounds of formula I are generally applied to the plant or to the locus thereof at rates of application of from 0.001 to 4 kg/ha, especially from 0.005 to 2 kg/ha. The concentration required to achieve the desired effect can be determined by experiment. It is dependent upon the nature of the action, the stage of development of the cultivated plant and of the weed and on the application (place, time, method) and may vary within wide limits as a function of those parameters.

The compounds of formula I are distinguished by herbicidal and growth-inhibiting properties, allowing them to be used in crops of useful plants, especially cereals, cotton, soybeans, sugar beet, sugar cane, plantation crops, rape, maize and rice, and also for non-selective weed control. The term “crops” is to be understood as including also crops that have been rendered tolerant to herbicides or classes of herbicides (such as, for example, HPPD inhibitors, ALS inhibitors, EPSPS (5-enol-pyrovyl-shikimate-3-phosphate-synthase) inhibitors, GS (glutamine synthetase) inhibitors) as a result of conventional methods of breeding or genetic engineering. An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding (mutagenesis) is Clearfield® summer rape (Canola). Examples of crops that have been rendered tolerant to herbicides or classes of herbicides by genetic engineering methods include glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady® and LibertyLink®.

Crops are also to be understood as being those which have been rendered resistant to harmful insects by genetic engineering methods, for example Bt maize (resistant to European corn borer), Bt cotton (resistant to cotton boll weevil) and also Bt potatoes (resistant to the Colorado beetle). Examples of Bt maize are the Bt 176 maize hybrids of NK® (Syngenta Seeds). The Bt toxin is a protein that is formed naturally by Bacillus thuringiensis soil bacteria. Examples of toxins, or transgenic plants able to synthesise such toxins, are described in EP-A-0 451 878, EP-A-0 374 753, WO 93/07278, WO 95/34656 and EP-A-0 427 529.

Plant crops or seed material thereof can be both herbicide-tolerant and at the same time resistant to insect feeding (“stacked” transgenic events).

The weeds to be controlled may be both monocotyledonous and dicotyledonous weeds, such as, for example, Stellaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica.

The compositions according to the invention may additionally comprise growth regulators, for example trinexapac (744), chlormequat chloride (129), clofencet (148), cyclanilide (170), ethephon (281), flurprimidol (355), gibberellic acid (379), inabenfide (421), maleic hydrazide (449), mefluidide (463), mepiquat chloride (465), paclobutrazol (548), prohexadione-calcium (595), uniconazole (746) or thidiazuron (703). It is also possible for a composition according to the invention to comprise fungicides, for example azoxystrobin (43), epoxiconazole (48), benomyl (60), bromuconazole (89), bitertanol (77), carbendazim (107), cyproconazole (189), cyprodinil (190), diclomezine (220), difenoconazole (228), diniconazole (247), epoxiconazole (48), ethirimol (284), etridiazole (294), fenarimol (300), fenbuconazole (302), fenpiclonil (311), fenpropidin (313), fenpropimorph (314), ferimzone (321), fludioxonil (334), fluquinconazole (349), flutolanil (360), flutriafol (361), imazalil (410), ipconazole (426), iprodione (428), isoprothiolane (432), kasugamycin (438), kresoxim-methyl (439), spiroxamine (441), mepronil (466), myclobutanil (505), nuarimol (528), pefurazoate (554), pencycuron (556), phthalide (576), probenazole (590), prochloraz (591), propiconazole (607), pyrazophos (619), pyroquilone (633), quinoxyfen (638), quintozene (639), tebuconazole (678), tetraconazole (695), thiabendazole (701), thifluzamide (705), triadimefon (720), triadimenol (721), tricyclazole (734), tridemorph (736), triflumizole (738), triforine (742), triticonazole (745) or vinclozolin (751). The number in brackets after each active ingredient refers to the entry number of that active ingredient in the Pesticide Manual, eleventh ed., British Crop Protection Council, 1997.

The following Examples further illustrate the invention but do not limit the invention.

PREPARATION EXAMPLE 1 Preparation of 2,3,4,4-tetrachloro-1,5-dimethyl-8-oxa-bicyclo-[3.2.1]octa-2,6-diene

6.49 g (67.48 mmol) of 2,5-dimethylfuran and 10 g (56.23 mmol) of tetrachlorocyclopropene are heated at boiling temperature in 70 ml of toluene for 16 hours. The toluene and excess 2,5-dimethylfuran are then removed under reduced pressure. The product, 14.77 g (95.9% of theory) of 2,3,4,4-tetrachloro-1,5-dimethyl-8-oxa-bicyclo[3.2.1]octa-2,6-diene, which remains behind in the form of an oil, can be transferred to the next reaction step without further purification (¹H NMR).

¹H NMR (300 MHz; CDCl₃) δ 6.50 (d, 1H); 6.15 (d, 1H); 1.82 (s, 3H); 1.63 (s, 3H).

PREPARATION EXAMPLE P2 Preparation of 3,4-dichloro-1,5-dimethyl-8-oxa-bicyclo[3.2.1]octa-3,6-dien-2-one

14 g (51.1 mmol) of unpurified 2,3,4,4-tetrachloro-1,5-dimethyl-8-oxa-bicyclo[3.2.1]octa-2,6-diene and 17.36 g (102.2 mmol) of silver nitrate are dissolved in 500 ml of acetone/water 1:1 mixture and heated for 15 hours at a temperature of 65-70° C. until the reaction of the reactants is complete (thin-layer chromatography (TLC) monitoring (mobile phase hexane/ethyl acetate 4:1)). After the reaction mixture has cooled to ambient temperature, solid sodium hydrogen carbonate is then stirred into the mixture in portions in order to neutralise the nitric acid. The precipitated silver bromide is filtered off and most of the acetone is distilled off under reduced pressure. The aqueous phase that remains behind is extracted three times with ethyl acetate. The organic extract is washed with water, dried over sodium sulfate and concentrated by evaporation. The oily residue is purified by means of silica gel chromatography (eluant gradient: 3-50% ethyl acetate in hexane). 6.1 g (54%) of pure 3,4-dichloro-1,5-dimethyl-8-oxa-bicyclo[3.2.1]octa-3,6-dien-2-one are obtained in the form of a pale yellow solid.

¹H NMR (300 MHz; CDCl₃) δ 6.65 (d, 1H); 6.23 (d, 1H); 1.72 (s, 3H); 1.61 (s, 3H).

PREPARATION EXAMPLE P3 Preparation of 3-chloro-1,5-dimethyl-4-methoxy-8-oxa-bicyclo-[3.2.1]octa-3,6-dien-2-one and 3-chloro-4,4-dimethoxy-1,5-dimethyl-8-oxa-bicyclo[3.2.1]oct-6-en-2-one

6.0 g (27.39 mmol) of 3,4-dichloro-1,5-dimethyl-8-oxa-bicyclo[3.2.1]octa-3,6-dien-2-one is introduced into 39 ml of anhydrous methanol. At a temperature of 0° C., the reaction mixture is further diluted dropwise with a solution of 15.2 ml of 5.4M sodium methanolate (82.17 mmol) and treated with 10 ml of absolute methanol. The reaction mixture is then heated to ambient temperature with 35 minutes' stirring. Using thin-layer chromatography (hexane/ethyl acetate 8:2) it can be established that reaction of the starting material is complete. The reaction solution is then concentrated under reduced pressure. The residue is then extracted by means of carbon tetrachloride against water. The aqueous phase is extracted a further three times using fresh carbon tetrachloride. The combined organic extracts are dried over sodium sulfate and concentrated by evaporation under reduced pressure; with ice-cooling, the oily product that remains behind crystallises out in the form of a ˜1:1 mixture. The mixture is separated by means of column chromatography on silica gel (eluant: gradient from 1-5% ethyl acetate/hexane). 3.1 g (52.9%) of pure 3-chloro-1,5-dimethyl-4-methoxy-8-oxa-bicyclo[3.2.1]octa-3,6-dien-2-one are isolated.

¹H NMR (300 MHz; CDCl₃) δ 6.48 (d, 1H); 6.24 (d, 1H); 4.24 (s, 3H); 1.60 (s, 3H); 1.56 (s, 3H).

A second fraction yields 3.17 g (46.9%) of pure 3-chloro-4,4-dimethoxy-1,5-dimethyl-8-oxa-bicyclo[3.2.1]oct-6-en-2-one.

¹H NMR (300 MHz; CDCl₃) δ 6.25 (d, 1H); 6.05 (d, 1H); 5.15 (s, 1H); 3.48 (s, 3H); 3.46 (s, 3H); 1.53 (s, 3H); 1.51 (s, 3H).

PREPARATION EXAMPLE P4 Preparation of 4,4-dimethoxy-1,5-dimethyl-8-oxa-bicyclo[3.2.1]oct-6-en-2-one

2.2 g (8.92 mmol) of 3-chloro-4,4-dimethoxy-1,5-dimethyl-8-oxa-bicyclo[3.2.1]oct-6-en-2-one in 240 ml of toluene are degassed, with heating at reflux temperature, and a catalytic amount of 66 mg of azaisobutyronitrile (AIBN) and a solution of 5.9 ml (22.3 mmol) of tributyltin hydride are added in succession. The reaction mixture is maintained at reflux temperature for a further 20 minutes to complete the reaction (TLC monitoring: hexane/ethyl acetate 4:1). The reaction mixture is then concentrated by evaporation under reduced pressure. The residue is then taken up in acetonitrile and the tin-containing residues are extracted by means of hexane. The acetonitrile phase is concentrated by evaporation in vacuo, 1.56 g (82.4% of theory) of 4,4-dimethoxy-1,5-dimethyl-8-oxa-bicyclo[3.2.1]oct-6-en-2-one remaining behind in the form of a yellow oil, which can be used for the next reaction step without further purification.

¹H NMR (300 MHz; CDCl₃) δ 6.22 (d, 1H); 5.90 (d, 1H); 3.41 (s, 3H); 3.25 (s, 3H); 2.92 and 2.84 (AB syst., 2H, J=16.5 Hz); 1.55 (s, 3H); 1.45 (s, 3H).

PREPARATION EXAMPLE P5 Preparation of 1,5-dimethyl-8-oxa-bicyclo[3.2.1]oct-6-ene-2,4-dione

1.61 g (7.59 mmol) of 4,4-dimethoxy-1,5-dimethyl-8-oxa-bicyclo[3.2.1]oct-6-en-2-one and 0.432 g (2.28 mmol) of p-toluenesulfonic acid are dissolved in a 2:1 mixture of acetone and water and heated for 50 minutes at a temperature of 70° C. (TLC monitoring: hexane/ethyl acetate 9:1). The acetone is then removed under reduced pressure. The aqueous phase is then adjusted to pH 9 with saturated sodium hydrogen carbonate solution and extracted three times with ethyl acetate to remove neutral components. The aqueous phase is then adjusted to pH 5 with dilute hydrochloric acid and extracted three times with fresh ethyl acetate. The organic phase is dried over sodium sulfate and concentrated by evaporation under reduced pressure, there being obtained 1.04 g (82.5%) of technically pure 1,5-dimethyl-8-oxa-bicyclo[3.2.1]oct-6-ene-2,4-dione in the form of a yellowish product, which can be used without further purification in the next reaction step to form compounds of formula I.

¹H NMR (300 MHz; CDCl₃) δ 6.46 (d, 1H); 6.23 (d, 1H); 5.54 (hept., 1H); 1.58 (d, 6H); 1.40 (d, 3H); 1.25 (d, 3H).

PREPARATION EXAMPLE P6 Preparation of 3-bromo-1,5-dimethyl-4-isopropoxy-8-oxa-bicyclo-[3.2.1]octa-3,6-dien-2-one

A solution of 2.74 g (8.9 mmol) of 3,4-dibromo-1,5-dimethyl-8-oxa-bicyclo[3.2.1]octa-3,6-dien-2-one (prepared according to Organic Lett. 4(12), 1997 (2002)) dissolved in 10 ml of tetrahydrofuran is added dropwise at ambient temperature to a solution of 5.4 ml (10.7 mmol) of 2M lithium isopropanolate diluted with 10 ml of tetrahydrofuran. The mixture is stirred for 3 hours at ambient temperature until the starting material has reacted completely (TLC monitoring: hexane/ethyl acetate/hexane 4:1). The reaction solution is then treated at a temperature of 0° C. with a 10% sodium dihydrogen phosphate solution (20 ml) and water (30 ml) and extracted three times with ethyl acetate. Drying over sodium sulfate and concentration by evaporation are carried out. For further purification, the dark oil so obtained is purified by chromatography over silica gel with 5% ethyl acetate in hexane. 1.73 g (68% of theory) of pure 3-bromo-1,5-dimethyl-4-isopropoxy-8-oxa-bicyclo[3.2.1]octa-3,6-dien-2-one are isolated.

¹H NMR (300 MHz; CDCl₃) δ 6.46 (d, 1H); 6.23 (d, 1H); 5.54 (hept., 1H); 1.58 (d, 6H); 1.40 (d, 3H); 1.25 (d, 3H).

PREPARATION EXAMPLE P7 Preparation of 3-bromo-4,4-(1′,2′-ethylenedioxy)-bicyclo[3.2.1]oct-6-en-2-one

A sodium glycolate solution is prepared by stirring 124 mg (5.4 mmol) of metallic sodium into 2.7 ml (42.42 mmol) of anhydrous ethylene glycol at ambient temperature and, when the sodium has completely dissolved, 1.5 ml of tetrahydrofuran are added. To the resulting monosodium glycolate solution there is then added dropwise a solution of 1 g (3.6 mmol) of 3,4-dibromo-bicyclo[3.2.1]octa-3,6-dien-2-one (prepared according to Organic Lett. 4(12), 1997 (2002)) dissolved in 5 ml of tetrahydrofuran. The reaction mixture is then stirred at ambient temperature for 90 minutes with TLC monitoring (mobile phase hexane/ethyl acetate 4:1). The reaction mixture is then treated with 8 ml of 10% sodium dihydrogen phosphate solution and extracted with ethyl acetate (3×). The organic phase is washed with water to remove ethylene glycol, then dried and concentrated by evaporation. 930 mg (˜100%) of 3-bromo-4,4-ethylenedioxy-bicyclo[3.2.1]oct-6-en-2-one are obtained in the form of a white solid.

¹H NMR (300 MHz; CDCl₃) δ 6.38 (m, 1H); 6.25 (m, 1H); 5.46 (s, 1H); 4.25 (m, 2H); 4.04 (m, 2H); 3.38 (m, 1H); 2.98 (m, 1H); 2.40 (m, 1H); 2.25 (m, 1H).

PREPARATION EXAMPLE P8 Preparation of 4,4-(1′,2′-ethylenedioxy)-bicyclo[3.2.1]oct-6-en-2-one

A degassed solution of 920 mg (3.55 mmol) of 3-bromo-4,4-(1′,2′-ethylenedioxy)-bicyclo-[3.2.1]oct-6-en-2-one in 90 ml of toluene is treated at boiling temperature in succession with a catalytic amount (30 mg) of AIBN and with 2.35 ml (8.88 mmol) of tributyltin hydride. To complete the reaction, the reaction mixture is maintained at reflux for a further 20 minutes, with TLC monitoring (mobile phase hexane/ethyl acetate 1:1). The reaction mixture is then concentrated by evaporation under reduced pressure. The residue is taken up in a small amount of acetonitrile and extracted five times with a small amount of hexane in order to remove tin-containing secondary products. The acetonitrile phase is then again concentrated by evaporation. 800 mg of 4,4-(1′,2′-ethylenedioxy)-bicyclo[3.2.1]oct-6-en-2-one are obtained in the form of a yellow oil, which can be transferred directly to the next reaction step without further purification.

¹H NMR (300 MHz; CDCl₃) δ 6.30 (m, 1H); 6.12 (m, 1H); 4.02-3.90 (m, 2×2H); 3.10 (m, 1H); 3.06 (d, 1H); 2.83 (m, 1H); 2.45 (d, 1H); 2.40-2.25 (m, 2×1H).

PREPARATION EXAMPLE P9 Bicyclo[3.2.1]oct-6-ene-2,4-dione

a) 640 mg (3.55 mmol) of 4,4-(1′,2′-ethylenedioxy)-bicyclo[3.2.1]oct-6-en-2-one are heated for 16 hours at a temperature of 70° C. in the presence of 200 mg of p-toluenesulfonic acid in a 2:1 mixture of acetone and water. After hydrolysis is complete (TLC monitoring: ethyl acetate/hexane 1:1), the acetone is distilled off under reduced pressure and the aqueous phase is adjusted to pH 9 with saturated sodium hydrogen carbonate solution. After extraction of the aqueous phase three times with ethyl acetate, it is acidified to pH 5 with dilute hydrochloric acid. Extraction is carried out three times with fresh ethyl acetate, followed by drying over sodium sulfate and concentration by evaporation in vacuo. 364 mg (75%) of pure bicyclo[3.2.1]oct-6-ene-2,4-dione are obtained in the form of a yellow oil for further reaction to form compounds of formula I.

¹H NMR (300 MHz; CDCl₃) δ 6.22 (m, 2H); 3.50 (d, 1H); 3.45 (m, 2H); 3.22 (d, 1H); 2.60-2.45 (m, 2×1H).

b) One-pot process: 100 mg (0.39 mmol) of 3-bromo-4,4-(1′,2′-ethylenedioxy)-bicyclo[3.2.1]-oct-6-en-2-one are taken up in concentrated acetic acid and treated at ambient temperature with 80 mg (1.16 mmol) of zinc powder. The progress of the reaction is monitored by means of thin-layer chromatography (mobile phase: hexane/ethyl acetate 1:1). When after 2 hours brominated starting material can no longer be detected, the reaction mixture is heated continuously at a temperature of 95° C. After a further 2 hours, according to thin-layer chromatography all the reference material 4,4-(1′,2′-ethylenedioxy)-bicyclo[3.2.1]oct-6-en-2-one has reacted. The reaction mixture is filtered and concentrated in vacuo. The residue is treated with saturated sodium hydrogen carbonate solution and extracted three times with ethyl acetate. The alkaline aqueous phase is adjusted to pH 3-4 with dilute hydrochloric acid and extracted three times with fresh ethyl acetate. After drying of the organic phase over sodium sulfate and subsequent concentration by evaporation, 45 mg (85% of theory) of technically pure bicyclo[3.2.1]oct-6-ene-2,4-dione are obtained.

PREPARATION EXAMPLE P10 Preparation of 3-[2-(2-methoxy-ethoxymethyl)-6-trifluoromethyl-pyridine-3-carbonyl]-1,5-dimethyl-8-oxa-bicyclo[3.2.1]oct-6-ene-2,4-dione

146 mg (0.879 mmol) of 1,5-dimethyl-8-oxa-bicyclo[3.2.1]oct-6-ene-2,4-dione and 245 mg (0.879 mmol) of 2-(2-methoxy-ethoxymethyl)-6-trifluoromethyl-nicotinic acid (preparation as described in WO 01/94339) are dissolved in 29 ml of acetonitrile and treated at ambient temperature with 199 mg (0.966 mmol) of dicyclohexylcarbodiimide. The reaction mixture is stirred for 2 hours and then 0.184 ml (1.318 mmol) of triethylamine and 0.08 ml (0.879 mmol) of acetone cyanohydrin are added. Stirring is carried out for a further 16 hours at ambient temperature, followed by concentration under reduced pressure. The residue that remains behind is chromatographed over silica gel (eluant: toluene/ethanol/dioxane/triethylamine/water 20:8:4:4:1). The product-containing fraction is concentrated. The oily residue is again dissolved in fresh ethyl acetate and washed with 10 ml of dilute hydrochloric acid (pH 1), and then with water (2×) and sodium chloride solution (2×). After the solution has been dried over sodium sulfate and concentrated by evaporation under reduced pressure, 128 mg (34%) of 3-[2-(2-methoxy-ethoxymethyl)-6-trifluoromethyl-pyridine-3-carbonyl]-1,5-dimethyl-8-oxa-bicyclo[3.2.1]oct-6-ene-2,4-dione are obtained in the form of a yellow oil.

¹H NMR (300 MHz; CDCl₃) δ 16.1 (br. s, 1H); 7.68 (m, 2×1H); 6.29 (d, 1H); 6.22 (d, 1H); 4.72 (m, 2H); 3.48 (m, 2H); 3.37 (m, 2H); 3.32 (s, 3H); 1.68 (s, 3H); 1.48 (s, 3H).

PREPARATION EXAMPLE P11 3-Chloro-bicyclo[3.2.2]non-6-ene-2,4-dione

0.7 g (2.7 mmol) of 2,3,4,4-tetrachloro-bicyclo[3.2.2]nona-2,6-diene (known from U.S. Pat. No. 3,538,117) is heated in a mixture of 1 ml of trifluoroacetic acid, 4 ml of acetic acid and 1 ml of water for 18 hours at a temperature of 70° C. The cooled reaction solution is then taken up in diethyl ether and extracted first with water and then with saturated sodium chloride solution. After chromatographic purification (ethyl acetate/hexane 1:4), 0.33 g of 3-chloro-bicyclo-[3.2.2]non-6-ene-2,4-dione is obtained as a tautomeric mixture of the forms Da and Db.

¹H-NMR (300 MHz; CDCl₃) δ 8.58 (b, 1H); 6.38 (m, 2H); 3.78 (m, 2H); 2.05 to 1.80 (m, 4H); tautomeric form Db.

PREPARATION EXAMPLE P12 Bicyclo[3.2.2]non-6ene-2,4-dione

0.19 g (1 mmol) of 3-chloro-bicyclo[3.2.2]non-6-ene-2,4-dione is treated in the presence of 4 ml of acetic acid with 0.27 g (4 mmol) of zinc and the mixture is heated for 3 hours at a temperature of 95° C. The cooled reaction mixture is then extracted with ethyl acetate against water and then washed again with saturated sodium chloride solution. 0.14 g of amorphous bicyclo[3.2.2]non-6-ene-2,4-dione is obtained as tautomeric form Da.

¹H-NMR (300 MHz; CDCl₃) δ 6.22 (m, 2H); 3.58 to 3.51 (m, 2H); 2.12 (m, 2H); 1.92 (m, 2H).

PREPARATION EXAMPLE P13 5-Bromo-7,8-dioxo-bicyclo[2.2.2]oct-5-ene-2-carboxylic acid methyl ester

3 g (9.4 mmol) of 5-bromo-8,8-dimethoxy-7-oxo-bicyclo[2.2.2]oct-5-ene-2-carboxylic acid methyl ester (J.O.C. (202), 67, 6493) are stirred in a mixture of 15 ml of trifluoroacetic acid and 1 ml of water for 12 hours at room temperature. Extraction is then carried out with dichloromethane against water. The organic phase is dried over sodium sulfate and yields, after removal of the solvent, the 5-bromo-7,8-dioxo-bicyclo[2.2.2]oct-5-ene-2-carboxylic acid methyl ester in the form of an orange-coloured oil and as a pure isomer.

¹H-NMR (300 MHz; CDCl₃) δ 6.62 (d, 1H); 3.97 (d, 1H); 3.80 (s, 3H); 3.70 (m, 1H); 3.20 (d, 1H); 2.63 (m, 1H); 2.40 (m, 1H).

PREPARATION EXAMPLE P14 8-Bromo-2,4-dioxo-bicyclo[3.2.2]non-8-ene-6-carboxylic acid methyl ester

4.2 ml of trimethylsilyl-diazomethane are added dropwise at a temperature of −10° C. to a solution of 1.91 g (7 mmol) of 5-bromo-7,8-dioxo-bicyclo[2.2.2]oct-5-ene-2-carboxylic acid methyl ester in 20 ml of dichloromethane and 0.089 ml (0.7 mmol) of boron trifluoride etherate. The cooling is removed and the reaction mixture is stirred for 4 hours at a temperature of 20° C. The reaction solution is then extracted with water, the organic phase is dried over sodium sulfate and concentrated by evaporation using a rotary evaporator, and the residue is purified by silica gel chromatography. An isomer of 8-bromo-2,4-dioxo-bicyclo[3.2.2]non-8-ene-6-carboxylic acid methyl ester is obtained.

¹H-NMR (300 MHz; CDCl₃) δ 6.42 (d, 1H); 3.86 (d, 1H); 3.75 (d, 1H); 3.68 (s, 3H); 3.65 (m, 1H); 3.43 (d, 1H); 3.10 (m, 1H); 2.52 (m, 1H); 2.34 (m, 1H); tautomeric form Da.

PREPARATION EXAMPLE P15 3-(2-Methyl-6-difluoromethyl-pyridine-3-carbonyl)-2,4-dioxo-bicyclo[3.2.2]non-8-ene-6-carboxylic acid methyl ester

Catalytic amounts (10 mg) of azaisobutyronitrile are added to a solution of 0.10 g (0.24 mmol) of 8-bromo-3-(2-methyl-6-difluoromethyl-pyridine-3-carbonyl)-2,4-dioxo-bicyclo-[3.2.2]non-8-ene-6-carboxylic acid methyl ester (Example 1.1155) and 0.149 ml (0.48 mmol) of tris(trimethylsilyl)silane in 3.5 ml of toluene and the reaction mixture is stirred at a temperature of 80° C. 5 mg portions of fresh azaisobutyronitrile dissolved in a small amount of toluene are then added four times until, after 6 days, the reaction has come to a complete standstill (LC-MS monitoring). The solvent is then removed under reduced pressure and the residue is purified by silica gel chromatography (eluant: gradient mixture of ethyl acetate/tetrahydrofuran/hexane and 3% triethylamine). After removal of the solvents the triethyl-ammonium salt of 3-(2-methyl-6-difluoromethyl-pyridine-3-carbonyl)-2,4-dioxo-bicyclo-[3.2.2]non-8-ene-6-carboxylic acid methyl ester is obtained.

¹H-NMR (300 MHz; CDCl₃) δ 7.30 (m, 2H); 6.51 (t, 1H); 6.35 (m, 1H); 6.18 (m, 1H); 3.68 (m, 1H); 3.52 (s, 3H); 3.35 (m, 1H); 3.24 (m, 1H); 3.00 (q, 6H); 2.40 (s, 3H); 2.38 (m, 1H); 2.14 (m, 1H); 1.18 (t, 9H).

The following Tables 1 to 3 list preferred compounds of formula I. The linkage site of the substituent Z₁ to the pyridine ring is the unsaturated valency; the free bonds represent methyl groups. For example, in the group

the —CH₂ group at the nitrogen atom adjacent to the keto group is the linkage site; the free bond at the nitrogen atom represents methyl. That group can also be depicted as follows:

TABLE 1 Compounds of formula Ib: (Ib)

No. R₁ R₂ Z₁ R₃₀ X Y p Physical data 1.0000 H H CH₃ H F NSO₂CH₃ 0 1.0001 H H CH₃ H Cl NSO₂CH₃ 0 1.0002 H H CH₃ H H NSO₂CH₃ 0 1.0003 H H CH₃ CH₃ F NSO₂CH₃ 0 1.0004 H H CH₃ CH₃ Cl NSO₂CH₃ 0 1.0005 H H CH₃ CH₃ H NSO₂CH₃ 0 1.0006 H H CH₂CH₃ H F NSO₂CH₃ 0 1.0007 H H CH₂CH₃ H Cl NSO₂CH₃ 0 1.0008 H H CH₂CH₃ H H NSO₂CH₃ 0 1.0009 H H CH₂CH₂CH₃ H F NSO₂CH₃ 0 1.0010 H H CH₂CH₂CH₃ H Cl NSO₂CH₃ 0 1.0011 H H CH₂CH₂CH₃ H H NSO₂CH₃ 0 1.0012 H H CH₂OCH₃ H F NSO₂CH₃ 0 1.0013 H H CH₂OCH₃ H Cl NSO₂CH₃ 0 1.0014 H H CH₂OCH₃ H H NSO₂CH₃ 0 1.0015 H H CH₂OCH₂CH₃ H F NSO₂CH₃ 0 1.0016 H H CH₂OCH₂CH₃ H Cl NSO₂CH₃ 0 1.0017 H H CH₂OCH₂CH₃ H H NSO₂CH₃ 0 1.0018 H H CH₂OCH₂CH₂OCH₃ H F NSO₂CH₃ 0 1.0019 H H CH₂OCH₂CH₂OCH₃ H Cl NSO₂CH₃ 0 1.0020 H H CH₂OCH₂CH₂OCH₃ H H NSO₂CH₃ 0 1.0021 H H CH₂OCH₂CH₂OCH₂CH₃ H F NSO₂CH₃ 0 1.0022 H H CH₂OCH₂CH₂OCH₂CH₃ H Cl NSO₂CH₃ 0 1.0023 H H CH₂OCH₂CH₂OCH₂CH₃ H H NSO₂CH₃ 0 1.0024 H H CH₂CH₂OCH₃ H F NSO₂CH₃ 0 1.0025 H H CH₂CH₂OCH₃ H Cl NSO₂CH₃ 0 1.0026 H H CH₂CH₂OCH₃ H H NSO₂CH₃ 0 1.0027 H H CH₂OCH₂C≡CH H F NSO₂CH₃ 0 1.0028 H H CH₂OCH₂C≡CH H Cl NSO₂CH₃ 0 1.0029 H H CH₂OCH₂C≡CH H H NSO₂CH₃ 0 1.0030 H H CH₂OCH₂C≡CCH₃ H F NSO₂CH₃ 0 1.0031 H H CH₂OCH₂C≡CCH₃ H Cl NSO₂CH₃ 0 1.0032 H H CH₂OCH₂C≡CCH₃ H H NSO₂CH₃ 0 1.0033 H H CH₂CH₂CH₂OCH₃ H F NSO₂CH₃ 0 1.0034 H H CH₂CH₂CH₂OCH₃ H Cl NSO₂CH₃ 0 1.0035 H H CH₂CH₂CH₂OCH₃ H H NSO₂CH₃ 0 1.0036 H H CH₂OCH₂OCH₃ H F NSO₂CH₃ 0 1.0037 H H CH₂OCH₂OCH₃ H Cl NSO₂CH₃ 0 1.0038 H H CH₂OCH₂OCH₃ H H NSO₂CH₃ 0 1.0039 H H CH₂N(CH₃)SO₂CH₃ H F NSO₂CH₃ 0 1.0040 H H CH₂N(CH₃)SO₂CH₃ H Cl NSO₂CH₃ 0 1.0041 H H CH₂N(CH₃)SO₂CH₃ H H NSO₂CH₃ 0 1.0042 H H CF₃ H F NSO₂CH₃ 0 1.0043 H H CF₃ H Cl NSO₂CH₃ 0 1.0044 H H CF₃ H H NSO₂CH₃ 0 1.0045 H H CH₂OCH₂CF₃ H F NSO₂CH₃ 0 1.0046 H H CH₂OCH₂CF₃ H Cl NSO₂CH₃ 0 1.0047 H H CH₂OCH₂CF₃ H H NSO₂CH₃ 0 1.0048 H H CH₂OCH₂Ph H F NSO₂CH₃ 0 1.0049 H H CH₂OCH₂Ph H Cl NSO₂CH₃ 0 1.0050 H H CH₂OCH₂Ph H H NSO₂CH₃ 0 1.0051 H H CH₂OCH₂CH═CH₂ H F NSO₂CH₃ 0 1.0052 H H CH₂OCH₂CH═CH₂ H Cl NSO₂CH₃ 0 1.0053 H H CH₂OCH₂CH═CH₂ H H NSO₂CH₃ 0 1.0054 H H

H F NSO₂CH₃ 0 1.0055 H H

H Cl NSO₂CH₃ 0 1.0056 H H

H H NSO₂CH₃ 0 1.0057 H H

H F NSO₂CH₃ 0 1.0058 H H

H Cl NSO₂CH₃ 0 1.0059 H H

H H NSO₂CH₃ 0 1.0060 H H

H F NSO₂CH₃ 0 1.0061 H H

H Cl NSO₂CH₃ 0 1.0062 H H

H H NSO₂CH₃ 0 1.0063 H H

H F NSO₂CH₃ 0 1.0064 H H

H Cl NSO₂CH₃ 0 1.0065 H H

H H NSO₂CH₃ 0 1.0066 H H

H F NSO₂CH₃ 0 1.0067 H H

H Cl NSO₂CH₃ 0 1.0068 H H

H H NSO₂CH₃ 0 1.0069 H H

H F NSO₂CH₃ 0 1.0070 H H

H Cl NSO₂CH₃ 0 1.0071 H H

H H NSO₂CH₃ 0 1.0072 H H CH₃ H F NSO₂CH₃ 1 1.0073 H H CH₂OCH₃ H F NSO₂CH₃ 1 1.0074 H H CH₂OCH₂CH₂OCH₃ H F NSO₂CH₃ 1 1.0075 H H CH₂CH₂CH₂OCH₃ H F NSO₂CH₃ 1 1.0076 H H CH₂CH₃ H F NSO₂CH₃ 1 1.0077 H H CH₃ H H NSO₂CH₃ 1 1.0078 H H CH₂OCH₃ H H NSO₂CH₃ 1 1.0079 H H CH₂OCH₂CH₂OCH₃ H H NSO₂CH₃ 1 1.0080 H H CH₂CH₂CH₂OCH₃ H H NSO₂CH₃ 1 1.0081 H H CH₂CH₃ H H NSO₂CH₃ 1 1.0082 CH₃ CH₃ CH₃ H F NSO₂CH₃ 0 1.0083 CH₃ CH₃ CH₃ H Cl NSO₂CH₃ 0 1.0084 CH₃ CH₃ CH₃ H H NSO₂CH₃ 0 1.0085 CH₃ CH₃ CH₃ CH₃ F NSO₂CH₃ 0 1.0086 CH₃ CH₃ CH₃ CH₃ Cl NSO₂CH₃ 0 1.0087 CH₃ CH₃ CH₃ CH₃ H NSO₂CH₃ 0 1.0088 CH₃ CH₃ CH₂CH₃ H F NSO₂CH₃ 0 1.0089 CH₃ CH₃ CH₂CH₃ H Cl NSO₂CH₃ 0 1.0090 CH₃ CH₃ CH₂CH₃ H H NSO₂CH₃ 0 1.0091 CH₃ CH₃ CH₂CH₂CH₃ H F NSO₂CH₃ 0 1.0092 CH₃ CH₃ CH₂CH₂CH₃ H Cl NSO₂CH₃ 0 1.0093 CH₃ CH₃ CH₂CH₂CH₃ H H NSO₂CH₃ 0 1.0094 CH₃ CH₃ CH₂OCH₃ H F NSO₂CH₃ 0 1.0095 CH₃ CH₃ CH₂OCH₃ H Cl NSO₂CH₃ 0 1.0096 CH₃ CH₃ CH₂OCH₃ H H NSO₂CH₃ 0 1.0097 CH₃ CH₃ CH₂OCH₂CH₃ H F NSO₂CH₃ 0 1.0098 CH₃ CH₃ CH₂OCH₂CH₃ H Cl NSO₂CH₃ 0 1.0099 CH₃ CH₃ CH₂OCH₂CH₃ H H NSO₂CH₃ 0 1.0100 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H F NSO₂CH₃ 0 1.0101 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H Cl NSO₂CH₃ 0 1.0102 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H H NSO₂CH₃ 0 1.0103 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ H F NSO₂CH₃ 0 1.0104 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ H Cl NSO₂CH₃ 0 1.0105 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ H H NSO₂CH₃ 0 1.0106 CH₃ CH₃ CH₂CH₂OCH₃ H F NSO₂CH₃ 0 1.0107 CH₃ CH₃ CH₂CH₂OCH₃ H Cl NSO₂CH₃ 0 1.0108 CH₃ CH₃ CH₂CH₂OCH₃ H H NSO₂CH₃ 0 1.0109 CH₃ CH₃ CH₂OCH₂C≡CH H F NSO₂CH₃ 0 1.0110 CH₃ CH₃ CH₂OCH₂C≡CH H Cl NSO₂CH₃ 0 1.0111 CH₃ CH₃ CH₂OCH₂C≡CH H H NSO₂CH₃ 0 1.0112 CH₃ CH₃ CH₂OCH₂C≡CCH₃ H F NSO₂CH₃ 0 1.0113 CH₃ CH₃ CH₂OCH₂C≡CCH₃ H Cl NSO₂CH₃ 0 1.0114 CH₃ CH₃ CH₂OCH₂C≡CCH₃ H H NSO₂CH₃ 0 1.0115 CH₃ CH₃ CH₂CH₂CH₂OCH₃ H F NSO₂CH₃ 0 1.0116 CH₃ CH₃ CH₂CH₂CH₂OCH₃ H Cl NSO₂CH₃ 0 1.0117 CH₃ CH₃ CH₂CH₂CH₂OCH₃ H H NSO₂CH₃ 0 1.0118 CH₃ CH₃ CH₂OCH₂OCH₃ H F NSO₂CH₃ 0 1.0119 CH₃ CH₃ CH₂OCH₂OCH₃ H Cl NSO₂CH₃ 0 1.0120 CH₃ CH₃ CH₂OCH₂OCH₃ H H NSO₂CH₃ 0 1.0121 CH₃ CH₃ CH₂N(CH₃)SO₂CH₃ H F NSO₂CH₃ 0 1.0122 CH₃ CH₃ CH₂N(CH₃)SO₂CH₃ H Cl NSO₂CH₃ 0 1.0123 CH₃ CH₃ CH₂N(CH₃)SO₂CH₃ H H NSO₂CH₃ 0 1.0124 CH₃ CH₃ CF₃ H F NSO₂CH₃ 0 1.0125 CH₃ CH₃ CF₃ H Cl NSO₂CH₃ 0 1.0126 CH₃ CH₃ CF₃ H H NSO₂CH₃ 0 1.0127 CH₃ CH₃ CH₂OCH₂CF₃ H F NSO₂CH₃ 0 1.0128 CH₃ CH₃ CH₂OCH₂CF₃ H Cl NSO₂CH₃ 0 1.0129 CH₃ CH₃ CH₂OCH₂CF₃ H H NSO₂CH₃ 0 1.0130 CH₃ CH₃ CH₂OCH₂Ph H F NSO₂CH₃ 0 1.0131 CH₃ CH₃ CH₂OCH₂Ph H Cl NSO₂CH₃ 0 1.0132 CH₃ CH₃ CH₂OCH₂Ph H H NSO₂CH₃ 0 1.0133 CH₃ CH₃ CH₂OCH₂CH═CH₂ H F NSO₂CH₃ 0 1.0134 CH₃ CH₃ CH₂OCH₂CH═CH₂ H Cl NSO₂CH₃ 0 1.0135 CH₃ CH₃ CH₂OCH₂CH═CH₂ H H NSO₂CH₃ 0 1.0136 CH₃ CH₃

H F NSO₂CH₃ 0 1.0137 CH₃ CH₃

H Cl NSO₂CH₃ 0 1.0138 CH₃ CH₃

H H NSO₂CH₃ 0 1.0139 CH₃ CH₃

H F NSO₂CH₃ 0 1.0140 CH₃ CH₃

H Cl NSO₂CH₃ 0 1.0141 CH₃ CH₃

H H NSO₂CH₃ 0 1.0142 CH₃ CH₃

H F NSO₂CH₃ 0 1.0143 CH₃ CH₃

H Cl NSO₂CH₃ 0 1.0144 CH₃ CH₃

H H NSO₂CH₃ 0 1.0145 CH₃ CH₃

H F NSO₂CH₃ 0 1.0146 CH₃ CH₃

H Cl NSO₂CH₃ 0 1.0147 CH₃ CH₃

H H NSO₂CH₃ 0 1.0148 CH₃ CH₃

H F NSO₂CH₃ 0 1.0149 CH₃ CH₃

H Cl NSO₂CH₃ 0 1.0150 CH₃ CH₃

H H NSO₂CH₃ 0 1.0151 CH₃ CH₃

H F NSO₂CH₃ 0 1.0152 CH₃ CH₃

H Cl NSO₂CH₃ 0 1.0153 CH₃ CH₃

H H NSO₂CH₃ 0 1.0154 CH₃ CH₃ CH₃ H F NSO₂CH₃ 1 1.0155 CH₃ CH₃ CH₂OCH₃ H F NSO₂CH₃ 1 1.0156 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H F NSO₂CH₃ 1 1.0157 CH₃ CH₃ CH₂CH₂CH₂OCH₃ H F NSO₂CH₃ I 1.0158 CH₃ CH₃ CH₂CH₃ H F NSO₂CH₃ 1 1.0159 CH₃ CH₃ CH₃ H H NSO₂CH₃ 1 1.0160 CH₃ CH₃ CH₂OCH₃ H H NSO₂CH₃ 1 1.0161 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H H NSO₂CH₃ 1 1.0162 CH₃ CH₃ CH₂CH₂CH₂OCH₃ H H NSO₂CH₃ 1 1.0163 CH₃ CH₃ CH₂CH₃ H H NSO₂CH₃ 1 1.0164 H CH₃ CH₃ H F NSO₂CH₃ 0 1.0165 H CH₃ CH₃ H Cl NSO₂CH₃ 0 1.0166 H CH₃ CH₃ H H NSO₂CH₃ 0 1.0167 H CH₃ CH₃ CH₃ F NSO₂CH₃ 0 1.0168 H CH₃ CH₃ CH₃ Cl NSO₂CH₃ 0 1.0169 H CH₃ CH₃ CH₃ H NSO₂CH₃ 0 1.0170 H CH₃ CH₂CH₃ H F NSO₂CH₃ 0 1.0171 H CH₃ CH₂CH₃ H Cl NSO₂CH₃ 0 1.0172 H CH₃ CH₂CH₃ H H NSO₂CH₃ 0 1.0173 H CH₃ CH₂CH₂CH₃ H F NSO₂CH₃ 0 1.0174 H CH₃ CH₂CH₂CH₃ H Cl NSO₂CH₃ 0 1.0175 H CH₃ CH₂CH₂CH₃ H H NSO₂CH₃ 0 1.0176 H CH₃ CH₂OCH₃ H F NSO₂CH₃ 0 1.0177 H CH₃ CH₂OCH₃ H Cl NSO₂CH₃ 0 1.0178 H CH₃ CH₂OCH₃ H H NSO₂CH₃ 0 1.0179 H CH₃ CH₂OCH₂CH₃ H F NSO₂CH₃ 0 1.0180 H CH₃ CH₂OCH₂CH₃ H Cl NSO₂CH₃ 0 1.0181 H CH₃ CH₂OCH₂CH₃ H H NSO₂CH₃ 0 1.0182 H CH₃ CH₂OCH₂CH₂OCH₃ H F NSO₂CH₃ 0 1.0183 H CH₃ CH₂OCH₂CH₂OCH₃ H Cl NSO₂CH₃ 0 1.0184 H CH₃ CH₂OCH₂CH₂OCH₃ H H NSO₂CH₃ 0 1.0185 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ H F NSO₂CH₃ 0 1.0186 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ H Cl NSO₂CH₃ 0 1.0187 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ H H NSO₂CH₃ 0 1.0188 H CH₃ CH₂CH₂OCH₃ H F NSO₂CH₃ 0 1.0189 H CH₃ CH₂CH₂OCH₃ H Cl NSO₂CH₃ 0 1.0190 H CH₃ CH₂CH₂OCH₃ H H NSO₂CH₃ 0 1.0191 H CH₃ CH₂OCH₂C≡CH H F NSO₂CH₃ 0 1.0192 H CH₃ CH₂OCH₂C≡CH H Cl NSO₂CH₃ 0 1.0193 H CH₃ CH₂OCH₂C≡CH H H NSO₂CH₃ 0 1.0194 H CH₃ CH₂OCH₂C≡CCH₃ H F NSO₂CH₃ 0 1.0195 H CH₃ CH₂OCH₂C≡CCH₃ H Cl NSO₂CH₃ 0 1.0196 H CH₃ CH₂OCH₂C≡CCH₃ H H NSO₂CH₃ 0 1.0197 H CH₃ CH₂CH₂CH₂OCH₃ H F NSO₂CH₃ 0 1.0198 H CH₃ CH₂CH₂CH₂OCH₃ H Cl NSO₂CH₃ 0 1.0199 H CH₃ CH₂CH₂CH₂OCH₃ H H NSO₂CH₃ 0 1.0200 H CH₃ CH₂OCH₂OCH₃ H F NSO₂CH₃ 0 1.0201 H CH₃ CH₂OCH₂OCH₃ H Cl NSO₂CH₃ 0 1.0202 H CH₃ CH₂OCH₂OCH₃ H H NSO₂CH₃ 0 1.0203 H CH₃ CH₂N(CH₃)SO₂CH₃ H F NSO₂CH₃ 0 1.0204 H CH₃ CH₂N(CH₃)SO₂CH₃ H Cl NSO₂CH₃ 0 1.0205 H CH₃ CH₂N(CH₃)SO₂CH₃ H H NSO₂CH₃ 0 1.0206 H CH₃ CF₃ H F NSO₂CH₃ 0 1.0207 H CH₃ CF₃ H Cl NSO₂CH₃ 0 1.0208 H CH₃ CF₃ H H NSO₂CH₃ 0 1.0209 H CH₃ CH₂OCH₂CF₃ H F NSO₂CH₃ 0 1.0210 H CH₃ CH₂OCH₂CF₃ H Cl NSO₂CH₃ 0 1.0211 H CH₃ CH₂OCH₂CF₃ H H NSO₂CH₃ 0 1.0212 H CH₃ CH₂OCH₂Ph H F NSO₂CH₃ 0 1.0213 H CH₃ CH₂OCH₂Ph H Cl NSO₂CH₃ 0 1.0214 H CH₃ CH₂OCH₂Ph H H NSO₂CH₃ 0 1.0215 H CH₃ CH₂OCH₂CH═CH₂ H F NSO₂CH₃ 0 1.0216 H CH₃ CH₂OCH₂CH═CH₂ H Cl NSO₂CH₃ 0 1.0217 H CH₃ CH₂OCH₂CH═CH₂ H H NSO₂CH₃ 0 1.0218 H CH₃

H F NSO₂CH₃ 0 1.0219 H CH₃

H Cl NSO₂CH₃ 0 1.0220 H CH₃

H H NSO₂CH₃ 0 1.0221 H CH₃

H F NSO₂CH₃ 0 1.0222 H CH₃

H Cl NSO₂CH₃ 0 1.0223 H CH₃

H H NSO₂CH₃ 0 1.0224 H CH₃

H F NSO₂CH₃ 0 1.0225 H CH₃

H Cl NSO₂CH₃ 0 1.0226 H CH₃

H H NSO₂CH₃ 0 1.0227 H CH₃

H F NSO₂CH₃ 0 1.0228 H CH₃

H Cl NSO₂CH₃ 0 1.0229 H CH₃

H H NSO₂CH₃ 0 1.0230 H CH₃

H F NSO₂CH₃ 0 1.0231 H CH₃

H Cl NSO₂CH₃ 0 1.0232 H CH₃

H H NSO₂CH₃ 0 1.0233 H CH₃

H F NSO₂CH₃ 0 1.0234 H CH₃

H Cl NSO₂CH₃ 0 1.0235 H CH₃

H H NSO₂CH₃ 0 1.0236 H CH₃ CH₃ H F NSO₂CH₃ 1 1.0237 H CH₃ CH₂OCH₃ H F NSO₂CH₃ 1 1.0238 H CH₃ CH₂OCH₂CH₂OCH₃ H F NSO₂CH₃ 1 1.0239 H CH₃ CH₂CH₂CH₂OCH₃ H F NSO₂CH₃ 1 1.0240 H CH₃ CH₂CH₃ H F NSO₂CH₃ 1 1.0241 H CH₃ CH₃ H H NSO₂CH₃ 1 1.0242 H CH₃ CH₂OCH₃ H H NSO₂CH₃ 1 1.0243 H CH₃ CH₂OCH₂CH₂OCH₃ H H NSO₂CH₃ 1 1.0244 H CH₃ CH₂CH₂CH₂OCH₃ H H NSO₂CH₃ 1 1.0245 H CH₃ CH₂CH₃ H H NSO₂CH₃ 1 1.0246 H H CH₂OCH₂CH₂OCH₃ H F O 0 1.0247 H H CH₂OCH₂CH₂OCH₃ H Cl O 0 1.0248 H H CH₂OCH₂CH₂OCH₃ H H O 0 1.0249 H H CH₂OCH₂CH₂OCH₂CH₃ H F O 0 1.0250 H H CH₂OCH₂CH₂OCH₂CH₃ H Cl O 0 1.0251 H H CH₂OCH₂CH₂OCH₂CH₃ H H O 0 1.0252 H H CH₂N(CH₃)SO₂CH₃ H F O 0 1.0253 H H CH₂N(CH₃)SO₂CH₃ H Cl O 0 1.0254 H H CH₂N(CH₃)SO₂CH₃ H H O 0 1.0255 H H CH₂OCH₂Ph H F O 0 1.0256 H H CH₂OCH₂Ph H Cl O 0 1.0257 H H CH₂OCH₂Ph H H O 0 1.0258 H H CH₂OCH₂CH₂OH H F O 0 1.0259 H H CH₂OCH₂CH₂OH H Cl O 0 1.0260 H H CH₂OCH₂CH₂OH H H O 0 1.0261 H H CH₂OCH₂CH₂Cl H F O 0 1.0262 H H CH₂OCH₂CH₂Cl H Cl O 0 1.0263 H H CH₂OCH₂CH₂Cl H H O 0 1.0264 H H CH₂OCH₂CF₃ H F O 0 1.0265 H H CH₂OCH₂CF₃ H Cl O 0 1.0266 H H CH₂OCH₂CF₃ H H O 0 1.0267 H H CH₂OCH₂CH═CH₂ H F O 0 1.0268 H H CH₂OCH₂CH═CH₂ H Cl O 0 1.0269 H H CH₂OCH₂CH═CH₂ H H O 0 1.0270 H H CH₂O(CO)CH₃ H F O 0 1.0271 H H CH₂O(CO)CH₃ H Cl O 0 1.0272 H H CH₂O(CO)CH₃ H H O 0 1.0273 H H CH₂OCH₂C≡CH H F O 0 1.0274 H H CH₂OCH₂C≡CH H Cl O 0 1.0275 H H CH₂OCH₂C≡CH H H O 0 1.0276 H H CH₂OCH₂C≡CCH₃ H F O 0 1.0277 H H CH₂OCH₂C≡CCH₃ H Cl O 0 1.0278 H H CH₂OCH₂C≡CCH₃ H H O 0 1.0279 H H

H F O 0 1.0280 H H

H Cl O 0 1.0281 H H

H H O 0 1.0282 H H

H F O 0 1.0283 H H

H Cl O 0 1.0284 H H

H H O 0 1.0285 H H

H F O 0 1.0286 H H

H Cl O 0 1.0287 H H

H H O 0 1.0288 H H

H F O 0 1.0289 H H

H Cl O 0 1.0290 H H

H H O 0 1.0291 H H

H F O 0 1.0292 H H

H Cl O 0 1.0293 H H

H H O 0 1.0294 H H

H F O 0 1.0295 H H

H Cl O 0 1.0296 H H

H H O 0 1.0297 H H CH₂OCH₂CH₂OCH₃ H F O 1 1.0298 H H CH₂OCH₂CH₂OCH₃ H H O 1 1.0299 H H CH₂OCH₂CH₂OCH₂CH₃ H F O 1 1.0300 H H CH₂OCH₂CH₂OCH₂CH₃ H H O 1 1.0301 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H F O 0 see Example P10 1.0302 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H Cl O 0 1.0303 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H H O 0 1.0304 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ H F O 0 1.0305 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ H Cl O 0 1.0306 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ H H O 0 1.0307 CH₃ CH₃ CH₂N(CH₃)SO₂CH₃ H F O 0 1.0308 CH₃ CH₃ CH₂N(CH₃)SO₂CH₃ H Cl O 0 1.0309 CH₃ CH₃ CH₂N(CH₃)SO₂CH₃ H H O 0 1.0310 CH₃ CH₃ CH₂OCH₂Ph H F O 0 1.0311 CH₃ CH₃ CH₂OCH₂Ph H Cl O 0 1.0312 CH₃ CH₃ CH₂OCH₂Ph H H O 0 1.0313 CH₃ CH₃ CH₂OCH₂CH₂OH H F O 0 1.0314 CH₃ CH₃ CH₂OCH₂CH₂OH H Cl O 0 1.0315 CH₃ CH₃ CH₂OCH₂CH₂OH H H O 0 1.0316 CH₃ CH₃ CH₂OCH₂CH₂Cl H F O 0 1.0317 CH₃ CH₃ CH₂OCH₂CH₂Cl H Cl O 0 1.0318 CH₃ CH₃ CH₂OCH₂CH₂Cl H H O 0 1.0319 CH₃ CH₃ CH₂OCH₂CF₃ H F O 0 1.0320 CH₃ CH₃ CH₂OCH₂CF₃ H Cl O 0 1.0321 CH₃ CH₃ CH₂OCH₂CF₃ H H O 0 1.0322 CH₃ CH₃ CH₂OCH₂CH═CH₂ H F O 0 1.0323 CH₃ CH₃ CH₂OCH₂CH═CH₂ H Cl O 0 1.0324 CH₃ CH₃ CH₂OCH₂CH═CH₂ H H O 0 1.0325 CH₃ CH₃ CH₂O(CO)CH₃ H F O 0 1.0326 CH₃ CH₃ CH₂O(CO)CH₃ H Cl O 0 1.0327 CH₃ CH₃ CH₂O(CO)CH₃ H H O 0 1.0328 CH₃ CH₃ CH₂OCH₂C≡CH H F O 0 1.0329 CH₃ CH₃ CH₂OCH₂C≡CH H Cl O 0 1.0330 CH₃ CH₃ CH₂OCH₂C≡CH H H O 0 1.0331 CH₃ CH₃ CH₂OCH₂C≡CCH₃ H F O 0 1.0332 CH₃ CH₃ CH₂OCH₂C≡CCH₃ H Cl O 0 1.0333 CH₃ CH₃ CH₂OCH₂C≡CCH₃ H H O 0 1.0334 CH₃ CH₃

H F O 0 1.0335 CH₃ CH₃

H Cl O 0 1.0336 CH₃ CH₃

H H O 0 1.0337 CH₃ CH₃

H F O 0 1.0338 CH₃ CH₃

H Cl O 0 1.0339 CH₃ CH₃

H H O 0 1.0340 CH₃ CH₃

H F O 0 1.0341 CH₃ CH₃

H Cl O 0 1.0342 CH₃ CH₃

H H O 0 1.0343 CH₃ CH₃

H F O 0 1.0344 CH₃ CH₃

H Cl O 0 1.0345 CH₃ CH₃

H H O 0 1.0346 CH₃ CH₃

H F O 0 1.0347 CH₃ CH₃

H Cl O 0 1.0348 CH₃ CH₃

H H O 0 1.0349 CH₃ CH₃

H F O 0 1.0350 CH₃ CH₃

H Cl O 0 1.0351 CH₃ CH₃

H H O 0 1.0352 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H F O 1 1.0353 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H H O 1 1.0354 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ H F O 1 1.0355 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ H H O 1 1.0356 H CH₃ CH₂OCH₂CH₂OCH₃ H F O 0 1.0357 H CH₃ CH₂OCH₂CH₂OCH₃ H Cl O 0 1.0358 H CH₃ CH₂OCH₂CH₂OCH₃ H H O 0 1.0359 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ H F O 0 1.0360 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ H Cl O 0 1.0361 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ H H O 0 1.0362 H CH₃ CH₂N(CH₃)SO₂CH₃ H F O 0 1.0363 H CH₃ CH₂N(CH₃)SO₂CH₃ H Cl O 0 1.0364 H CH₃ CH₂N(CH₃)SO₂CH₃ H H O 0 1.0365 H CH₃ CH₂OCH₂Ph H F O 0 1.0366 H CH₃ CH₂OCH₂Ph H Cl O 0 1.0367 H CH₃ CH₂OCH₂Ph H H O 0 1.0368 H CH₃ CH₂OCH₂CH₂OH H F O 0 1.0369 H CH₃ CH₂OCH₂CH₂OH H Cl O 0 1.0370 H CH₃ CH₂OCH₂CH₂OH H H O 0 1.0371 H CH₃ CH₂OCH₂CH₂Cl H F O 0 1.0372 H CH₃ CH₂OCH₂CH₂Cl H Cl O 0 1.0373 H CH₃ CH₂OCH₂CH₂Cl H H O 0 1.0374 H CH₃ CH₂OCH₂CF₃ H F O 0 1.0375 H CH₃ CH₂OCH₂CF₃ H Cl O 0 1.0376 H CH₃ CH₂OCH₂CF₃ H H O 0 1.0377 H CH₃ CH₂OCH₂CH═CH₂ H F O 0 1.0378 H CH₃ CH₂OCH₂CH═CH₂ H Cl O 0 1.0379 H CH₃ CH₂OCH₂CH═CH₂ H H O 0 1.0380 H CH₃ CH₂O(CO)CH₃ H F O 0 1.0381 H CH₃ CH₂O(CO)CH₃ H Cl O 0 1.0382 H CH₃ CH₂O(CO)CH₃ H H O 0 1.0383 H CH₃ CH₂OCH₂C≡CH H F O 0 1.0384 H CH₃ CH₂OCH₂C≡CH H Cl O 0 1.0385 H CH₃ CH₂OCH₂C≡CH H H O 0 1.0386 H CH₃ CH₂OCH₂C≡CCH₃ H F O 0 1.0387 H CH₃ CH₂OCH₂C≡CCH₃ H Cl O 0 1.0388 H CH₃ CH₂OCH₂C≡CCH₃ H H O 0 1.0389 H CH₃

H F O 0 1.0390 H CH₃

H Cl O 0 1.0391 H CH₃

H H O 0 1.0392 H CH₃

H F O 0 1.0393 H CH₃

H Cl O 0 1.0394 H CH₃

H H O 0 1.0395 H CH₃

H F O 0 1.0396 H CH₃

H Cl O 0 1.0397 H CH₃

H H O 0 1.0398 H CH₃

H F O 0 1.0399 H CH₃

H Cl O 0 1.0400 H CH₃

H H O 0 1.0401 H CH₃

H F O 0 1.0402 H CH₃

H Cl O 0 1.0403 H CH₃

H H O 0 1.0404 H CH₃

H F O 0 1.0405 H CH₃

H Cl O 0 1.0406 H CH₃

H H O 0 1.0407 H CH₃ CH₂OCH₂CH₂OCH₃ H F O 1 1.0408 H CH₃ CH₂OCH₂CH₂OCH₃ H H O 1 1.0409 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ H F O 1 1.0410 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ H H O 1 1.0411 H H CH₂OCH₂CH₂OCH₃ H F CH₂ 0 ¹H NMR (300 MHz; CDCl₃) δ 17.0 (broad s, 1H); 7.62 (s, 2H); 6.47 (m, 1H); 6.35 (m, 1H); 4.73 (m, 2H); 3.50 (m, 3H); 3.39 (m, 2H); 3.31 (s, 3H); 3.30 (m, 1H); 2.72-2.50 (m, 2H). 1.0412 H H CH₂OCH₂CH₂OCH₃ H Cl CH₂ 0 1.0413 H H CH₂OCH₂CH₂OCH₃ H H CH₂ 0 1.0414 H H CH₂OCH₂CH₂OCH₂CH₃ H F CH₂ 0 1.0415 H H CH₂OCH₂CH₂OCH₂CH₃ H Cl CH₂ 0 1.0416 H H CH₂OCH₂CH₂OCH₂CH₃ H H CH₂ 0 1.0417 H H CH₂N(CH₃)SO₂CH₃ H F CH₂ 0 1.0418 H H CH₂N(CH₃)SO₂CH₃ H Cl CH₂ 0 1.0419 H H CH₂N(CH₃)SO₂CH₃ H H CH₂ 0 1.0420 H H CH₂OCH₂Ph H F CH₂ 0 1.0421 H H CH₂OCH₂Ph H Cl CH₂ 0 1.0422 H H CH₂OCH₂Ph H H CH₂ 0 1.0423 H H CH₂OCH₂CH₂OH H F CH₂ 0 1.0424 H H CH₂OCH₂CH₂OH H Cl CH₂ 0 1.0425 H H CH₂OCH₂CH₂OH H H CH₂ 0 1.0426 H H CH₂OCH₂CH₂Cl H F CH₂ 0 1.0427 H H CH₂OCH₂CH₂Cl H Cl CH₂ 0 1.0428 H H CH₂OCH₂CH₂Cl H H CH₂ 0 1.0429 H H CH₂OCH₂CF₃ H F CH₂ 0 1.0430 H H CH₂OCH₂CF₃ H Cl CH₂ 0 1.0431 H H CH₂OCH₂CF₃ H H CH₂ 0 1.0432 H H CH₂OCH₂CH═CH₂ H F CH₂ 0 1.0433 H H CH₂OCH₂CH═CH₂ H Cl CH₂ 0 1.0434 H H CH₂OCH₂CH═CH₂ H H CH₂ 0 1.0435 H H CH₂O(CO)CH₃ H F CH₂ 0 1.0436 H H CH₂O(CO)CH₃ H Cl CH₂ 0 1.0437 H H CH₂O(CO)CH₃ H H CH₂ 0 1.0438 H H CH₂OCH₂C≡CH H F CH₂ 0 1.0439 H H CH₂OCH₂C≡CH H Cl CH₂ 0 1.0440 H H CH₂OCH₂C≡CH H H CH₂ 0 1.0441 H H CH₂OCH₂C≡CCH₃ H F CH₂ 0 1.0442 H H CH₂OCH₂C≡CCH₃ H Cl CH₂ 0 1.0443 H H CH₂OCH₂C≡CCH₃ H H CH₂ 0 1.0444 H H

H F CH₂ 0 1.0445 H H

H Cl CH₂ 0 1.0446 H H

H H CH₂ 0 1.0447 H H

H F CH₂ 0 1.0448 H H

H Cl CH₂ 0 1.0449 H H

H H CH₂ 0 1.0450 H H

H F CH₂ 0 1.0451 H H

H Cl CH₂ 0 1.0452 H H

H H CH₂ 0 1.0453 H H

H F CH₂ 0 1.0454 H H

H Cl CH₂ 0 1.0455 H H

H H CH₂ 0 1.0456 H H

H F CH₂ 0 1.0457 H H

H Cl CH₂ 0 1.0458 H H

H H CH₂ 0 1.0459 H H

H F CH₂ 0 1.0460 H H

H Cl CH₂ 0 1.0461 H H

H H CH₂ 0 1.0462 H H CH₂OCH₂CH₂OCH₃ H F CH₂ 1 1.0463 H H CH₂OCH₂CH₂OCH₃ H H CH₂ 1 1.0464 H H CH₂OCH₂CH₂OCH₂CH₃ H F CH₂ 1 1.0465 H H CH₂OCH₂CH₂OCH₂CH₃ H H CH₂ 1 1.0466 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H F CH₂ 0 1.0467 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H Cl CH₂ 0 1.0468 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H H CH₂ 0 1.0469 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ H F CH₂ 0 1.0470 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ H Cl CH₂ 0 1.0471 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ H H CH₂ 0 1.0472 CH₃ CH₃ CH₂N(CH₃)SO₂CH₃ H F CH₂ 0 1.0473 CH₃ CH₃ CH₂N(CH₃)SO₂CH₃ H Cl CH₂ 0 1.0474 CH₃ CH₃ CH₂N(CH₃)SO₂CH₃ H H CH₂ 0 1.0475 CH₃ CH₃ CH₂OCH₂Ph H F CH₂ 0 1.0476 CH₃ CH₃ CH₂OCH₂Ph H Cl CH₂ 0 1.0477 CH₃ CH₃ CH₂OCH₂Ph H H CH₂ 0 1.0478 CH₃ CH₃ CH₂OCH₂CH₂OH H F CH₂ 0 1.0479 CH₃ CH₃ CH₂OCH₂CH₂OH H Cl CH₂ 0 1.0480 CH₃ CH₃ CH₂OCH₂CH₂OH H H CH₂ 0 1.0481 CH₃ CH₃ CH₂OCH₂CH₂Cl H F CH₂ 0 1.0482 CH₃ CH₃ CH₂OCH₂CH₂Cl H Cl CH₂ 0 1.0483 CH₃ CH₃ CH₂OCH₂CH₂Cl H H CH₂ 0 1.0484 CH₃ CH₃ CH₂OCH₂CF₃ H F CH₂ 0 1.0485 CH₃ CH₃ CH₂OCH₂CF₃ H Cl CH₂ 0 1.0486 CH₃ CH₃ CH₂OCH₂CF₃ H H CH₂ 0 1.0487 CH₃ CH₃ CH₂OCH₂CH═CH₂ H F CH₂ 0 1.0488 CH₃ CH₃ CH₂OCH₂CH═CH₂ H Cl CH₂ 0 1.0489 CH₃ CH₃ CH₂OCH₂CH═CH₂ H H CH₂ 0 1.0490 CH₃ CH₃ CH₂O(CO)CH₃ H F CH₂ 0 1.0491 CH₃ CH₃ CH₂O(CO)CH₃ H Cl CH₂ 0 1.0492 CH₃ CH₃ CH₂O(CO)CH₃ H H CH₂ 0 1.0493 CH₃ CH₃ CH₂OCH₂C≡CH H F CH₂ 0 1.0494 CH₃ CH₃ CH₂OCH₂C≡CH H Cl CH₂ 0 1.0495 CH₃ CH₃ CH₂OCH₂C≡CH H H CH₂ 0 1.0496 CH₃ CH₃ CH₂OCH₂C≡CCH₃ H F CH₂ 0 1.0497 CH₃ CH₃ CH₂OCH₂C≡CCH₃ H Cl CH₂ 0 1.0498 CH₃ CH₃ CH₂OCH₂C≡CCH₃ H H CH₂ 0 1.0499 CH₃ CH₃

H F CH₂ 0 1.0500 CH₃ CH₃

H Cl CH₂ 0 1.0501 CH₃ CH₃

H H CH₂ 0 1.0502 CH₃ CH₃

H F CH₂ 0 1.0503 CH₃ CH₃

H Cl CH₂ 0 1.0504 CH₃ CH₃

H H CH₂ 0 1.0505 CH₃ CH₃

H F CH₂ 0 1.0506 CH₃ CH₃

H Cl CH₂ 0 1.0507 CH₃ CH₃

H H CH₂ 0 1.0508 CH₃ CH₃

H F CH₂ 0 1.0509 CH₃ CH₃

H Cl CH₂ 0 1.0510 CH₃ CH₃

H H CH₂ 0 1.0511 CH₃ CH₃

H F CH₂ 0 1.0512 CH₃ CH₃

H Cl CH₂ 0 1.0513 CH₃ CH₃

H H CH₂ 0 1.0514 CH₃ CH₃

H F CH₂ 0 1.0515 CH₃ CH₃

H Cl CH₂ 0 1.0516 CH₃ CH₃

H H CH₂ 0 1.0517 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H F CH₂ 1 1.0518 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H H CH₂ 1 1.0519 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ H F CH₂ 1 1.0520 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ H H CH₂ 1 1.0521 H CH₃ CH₂OCH₂CH₂OCH₃ H F CH₂ 0 1.0522 H CH₃ CH₂OCH₂CH₂OCH₃ H Cl CH₂ 0 1.0523 H CH₃ CH₂OCH₂CH₂OCH₃ H H CH₂ 0 1.0524 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ H F CH₂ 0 1.0525 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ H Cl CH₂ 0 1.0526 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ H H CH₂ 0 1.0527 H CH₃ CH₂N(CH₃)SO₂CH₃ H F CH₂ 0 1.0528 H CH₃ CH₂N(CH₃)SO₂CH₃ H Cl CH₂ 0 1.0529 H CH₃ CH₂N(CH₃)SO₂CH₃ H H CH₂ 0 1.0530 H CH₃ CH₂OCH₂Ph H F CH₂ 0 1.0531 H CH₃ CH₂OCH₂Ph H Cl CH₂ 0 1.0532 H CH₃ CH₂OCH₂Ph H H CH₂ 0 1.0533 H CH₃ CH₂OCH₂CH₂OH H F CH₂ 0 1.0534 H CH₃ CH₂OCH₂CH₂OH H Cl CH₂ 0 1.0535 H CH₃ CH₂OCH₂CH₂OH H H CH₂ 0 1.0536 H CH₃ CH₂OCH₂CH₂Cl H F CH₂ 0 1.0537 H CH₃ CH₂OCH₂CH₂Cl H Cl CH₂ 0 1.0538 H CH₃ CH₂OCH₂CH₂Cl H H CH₂ 0 1.0539 H CH₃ CH₂OCH₂CF₃ H F CH₂ 0 1.0540 H CH₃ CH₂OCH₂CF₃ H Cl CH₂ 0 1.0541 H CH₃ CH₂OCH₂CF₃ H H CH₂ 0 1.0542 H CH₃ CH₂OCH₂CH═CH₂ H F CH₂ 0 1.0543 H CH₃ CH₂OCH₂CH═CH₂ H Cl CH₂ 0 1.0544 H CH₃ CH₂OCH₂CH═CH₂ H H CH₂ 0 1.0545 H CH₃ CH₂O(CO)CH₃ H F CH₂ 0 1.0546 H CH₃ CH₂O(CO)CH₃ H Cl CH₂ 0 1.0547 H CH₃ CH₂O(CO)CH₃ H H CH₂ 0 1.0548 H CH₃ CH₂OCH₂C≡CH H F CH₂ 0 1.0549 H CH₃ CH₂OCH₂C≡CH H Cl CH₂ 0 1.0550 H CH₃ CH₂OCH₂C≡CH H H CH₂ 0 1.0551 H CH₃ CH₂OCH₂C≡CCH₃ H F CH₂ 0 1.0552 H CH₃ CH₂OCH₂C≡CCH₃ H Cl CH₂ 0 1.0553 H CH₃ CH₂OCH₂C≡CCH₃ H H CH₂ 0 1.0554 H CH₃

H F CH₂ 0 1.0555 H CH₃

H Cl CH₂ 0 1.0556 H CH₃

H H CH₂ 0 1.0557 H CH₃

H F CH₂ 0 1.0558 H CH₃

H Cl CH₂ 0 1.0559 H CH₃

H H CH₂ 0 1.0560 H CH₃

H F CH₂ 0 1.0561 H CH₃

H Cl CH₂ 0 1.0562 H CH₃

H H CH₂ 0 1.0563 H CH₃

H F CH₂ 0 1.0564 H CH₃

H Cl CH₂ 0 1.0565 H CH₃

H H CH₂ 0 1.0566 H CH₃

H F CH₂ 0 1.0567 H CH₃

H Cl CH₂ 0 1.0568 H CH₃

H H CH₂ 0 1.0569 H CH₃

H F CH₂ 0 1.0570 H CH₃

H Cl CH₂ 0 1.0571 H CH₃

H H CH₂ 0 1.0572 H CH₃ CH₂OCH₂CH₂OCH₃ H F CH₂ 1 1.0573 H CH₃ CH₂OCH₂CH₂OCH₃ H H CH₂ 1 1.0574 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ H F CH₂ 1 1.0575 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ H H CH₂ 1 1.0576 H H CH₂OCH₂CH₂OCH₃ H F CH₂CH₂ 0 resin 1.0577 H H CH₂OCH₂CH₂OCH₃ H Cl CH₂CH₂ 0 1.0578 H H CH₂OCH₂CH₂OCH₃ H H CH₂CH₂ 0 1.0579 H H CH₂OCH₂CH₂OCH₂CH₃ H F CH₂CH₂ 0 1.0580 H H CH₂OCH₂CH₂OCH₂CH₃ H Cl CH₂CH₂ 0 1.0581 H H CH₂OCH₂CH₂OCH₂CH₃ H H CH₂CH₂ 0 1.0582 H H CH₂N(CH₃)SO₂CH₃ H F CH₂CH₂ 0 1.0583 H H CH₂N(CH₃)SO₂CH₃ H Cl CH₂CH₂ 0 1.0584 H H CH₂N(CH₃)SO₂CH₃ H H CH₂CH₂ 0 1.0585 H H CH₂OCH₂Ph H F CH₂CH₂ 0 1.0586 H H CH₂OCH₂Ph H Cl CH₂CH₂ 0 1.0587 H H CH₂OCH₂Ph H H CH₂CH₂ 0 1.0588 H H CH₂OCH₂CH₂OH H F CH₂CH₂ 0 1.0589 H H CH₂OCH₂CH₂OH H Cl CH₂CH₂ 0 1.0590 H H CH₂OCH₂CH₂OH H H CH₂CH₂ 0 1.0591 H H CH₂OCH₂CH₂Cl H F CH₂CH₂ 0 1.0592 H H CH₂OCH₂CH₂Cl H Cl CH₂CH₂ 0 1.0593 H H CH₂OCH₂CH₂Cl H H CH₂CH₂ 0 1.0594 H H CH₂OCH₂CF₃ H F CH₂CH₂ 0 1.0595 H H CH₂OCH₂CF₃ H Cl CH₂CH₂ 0 1.0596 H H CH₂OCH₂CF₃ H H CH₂CH₂ 0 1.0597 H H CH₂OCH₂CH═CH₂ H F CH₂CH₂ 0 1.0598 H H CH₂OCH₂CH═CH₂ H Cl CH₂CH₂ 0 1.0599 H H CH₂OCH₂CH═CH₂ H H CH₂CH₂ 0 1.0600 H H CH₂O(CO)CH₃ H F CH₂CH₂ 0 1.0601 H H CH₂O(CO)CH₃ H Cl CH₂CH₂ 0 1.0602 H H CH₂O(CO)CH₃ H H CH₂CH₂ 0 1.0603 H H CH₂OCH₂C≡CH H F CH₂CH₂ 0 1.0604 H H CH₂OCH₂C≡CH H Cl CH₂CH₂ 0 1.0605 H H CH₂OCH₂C≡CH H H CH₂CH₂ 0 1.0606 H H CH₂OCH₂C≡CCH₃ H F CH₂CH₂ 0 1.0607 H H CH₂OCH₂C≡CCH₃ H Cl CH₂CH₂ 0 1.0608 H H CH₂OCH₂C≡CCH₃ H H CH₂CH₂ 0 1.0609 H H

H F CH₂CH₂ 0 1.0610 H H

H Cl CH₂CH₂ 0 1.0611 H H

H H CH₂CH₂ 0 1.0612 H H

H F CH₂CH₂ 0 1.0613 H H

H Cl CH₂CH₂ 0 1.0614 H H

H H CH₂CH₂ 0 1.0615 H H

H F CH₂CH₂ 0 1.0616 H H

H Cl CH₂CH₂ 0 1.0617 H H

H H CH₂CH₂ 0 1.0618 H H

H F CH₂CH₂ 0 1.0619 H H

H Cl CH₂CH₂ 0 1.0620 H H

H H CH₂CH₂ 0 1.0621 H H

H F CH₂CH₂ 0 1.0622 H H

H Cl CH₂CH₂ 0 1.0623 H H

H H CH₂CH₂ 0 1.0624 H H

H F CH₂CH₂ 0 1.0625 H H

H Cl CH₂CH₂ 0 1.0626 H H

H H CH₂CH₂ 0 1.0627 H H CH₂OCH₂CH₂OCH₃ H F CH₂CH₂ 1 1.0628 H H CH₂OCH₂CH₂OCH₃ H H CH₂CH₂ 1 1.0629 H H CH₂OCH₂CH₂OCH₂CH₃ H F CH₂CH₂ 1 1.0630 H H CH₂OCH₂CH₂OCH₂CH₃ H H CH₂CH₂ 1 1.0631 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H F CH₂CH₂ 0 1.0632 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H Cl CH₂CH₂ 0 1.0633 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H H CH₂CH₂ 0 1.0634 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ H F CH₂CH₂ 0 1.0635 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ H Cl CH₂CH₂ 0 1.0636 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ H H CH₂CH₂ 0 1.0637 CH₃ CH₃ CH₂N(CH₃)SO₂CH₃ H F CH₂CH₂ 0 1.0638 CH₃ CH₃ CH₂N(CH₃)SO₂CH₃ H Cl CH₂CH₂ 0 1.0639 CH₃ CH₃ CH₂N(CH₃)SO₂CH₃ H H CH₂CH₂ 0 1.0640 CH₃ CH₃ CH₂OCH₂Ph H F CH₂CH₂ 0 1.0641 CH₃ CH₃ CH₂OCH₂Ph H Cl CH₂CH₂ 0 1.0642 CH₃ CH₃ CH₂OCH₂Ph H H CH₂CH₂ 0 1.0643 CH₃ CH₃ CH₂OCH₂CH₂OH H F CH₂CH₂ 0 1.0644 CH₃ CH₃ CH₂OCH₂CH₂OH H Cl CH₂CH₂ 0 1.0645 CH₃ CH₃ CH₂OCH₂CH₂OH H H CH₂CH₂ 0 1.0646 CH₃ CH₃ CH₂OCH₂CH₂Cl H F CH₂CH₂ 0 1.0647 CH₃ CH₃ CH₂OCH₂CH₂Cl H Cl CH₂CH₂ 0 1.0648 CH₃ CH₃ CH₂OCH₂CH₂Cl H H CH₂CH₂ 0 1.0649 CH₃ CH₃ CH₂OCH₂CF₃ H F CH₂CH₂ 0 1.0650 CH₃ CH₃ CH₂OCH₂CF₃ H Cl CH₂CH₂ 0 1.0651 CH₃ CH₃ CH₂OCH₂CF₃ H H CH₂CH₂ 0 1.0652 CH₃ CH₃ CH₂OCH₂CH═CH₂ H F CH₂CH₂ 0 1.0653 CH₃ CH₃ CH₂OCH₂CH═CH₂ H Cl CH₂CH₂ 0 1.0654 CH₃ CH₃ CH₂OCH₂CH═CH₂ H H CH₂CH₂ 0 1.0655 CH₃ CH₃ CH₂O(CO)CH₃ H F CH₂CH₂ 0 1.0656 CH₃ CH₃ CH₂O(CO)CH₃ H Cl CH₂CH₂ 0 1.0657 CH₃ CH₃ CH₂O(CO)CH₃ H H CH₂CH₂ 0 1.0658 CH₃ CH₃ CH₂OCH₂C≡CH H F CH₂CH₂ 0 1.0659 CH₃ CH₃ CH₂OCH₂C≡CH H Cl CH₂CH₂ 0 1.0660 CH₃ CH₃ CH₂OCH₂C≡CH H H CH₂CH₂ 0 1.0661 CH₃ CH₃ CH₂OCH₂C≡CCH₃ H F CH₂CH₂ 0 1.0662 CH₃ CH₃ CH₂OCH₂C≡CCH₃ H 01 CH₂CH₂ 0 1.0663 CH₃ CH₃ CH₂OCH₂C≡CCH₃ H H CH₂CH₂ 0 1.0664 CH₃ CH₃

H F CH₂CH₂ 0 1.0665 CH₃ CH₃

H Cl CH₂CH₂ 0 1.0666 CH₃ CH₃

H H CH₂CH₂ 0 1.0667 CH₃ CH₃

H F CH₂CH₂ 0 1.0668 CH₃ CH₃

H Cl CH₂CH₂ 0 1.0669 CH₃ CH₃

H H CH₂CH₂ 0 1.0670 CH₃ CH₃

H F CH₂CH₂ 0 1.0671 CH₃ CH₃

H Cl CH₂CH₂ 0 1.0672 CH₃ CH₃

H H CH₂CH₂ 0 1.0673 CH₃ CH₃

H F CH₂CH₂ 0 1.0674 CH₃ CH₃

H Cl CH₂CH₂ 0 1.0675 CH₃ CH₃

H H CH₂CH₂ 0 1.0676 CH₃ CH₃

H F CH₂CH₂ 0 1.0677 CH₃ CH₃

H Cl CH₂CH₂ 0 1.0678 CH₃ CH₃

H H CH₂CH₂ 0 1.0679 CH₃ CH₃

H F CH₂CH₂ 0 1.0680 CH₃ CH₃

H Cl CH₂CH₂ 0 1.0681 CH₃ CH₃

H H CH₂CH₂ 0 1.0682 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H F CH₂CH₂ 1 1.0683 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H H CH₂CH₂ 1 1.0684 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ H F CH₂CH₂ 1 1.0685 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ H H CH₂CH₂ 1 1.0686 H CH₃ CH₂OCH₂CH₂OCH₃ H F CH₂CH₂ 0 1.0687 H CH₃ CH₂OCH₂CH₂OCH₃ H Cl CH₂CH₂ 0 1.0688 H CH₃ CH₂OCH₂CH₂OCH₃ H H CH₂CH₂ 0 1.0689 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ H F CH₂CH₂ 0 1.0690 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ H Cl CH₂CH₂ 0 1.0691 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ H H CH₂CH₂ 0 1.0692 H CH₃ CH₂N(CH₃)SO₂CH₃ H F CH₂CH₂ 0 1.0693 H CH₃ CH₂N(CH₃)SO₂CH₃ H Cl CH₂CH₂ 0 1.0694 H CH₃ CH₂N(CH₃)SO₂CH₃ H H CH₂CH₂ 0 1.0695 H CH₃ CH₂OCH₂Ph H F CH₂CH₂ 0 1.0696 H CH₃ CH₂OCH₂Ph H Cl CH₂CH₂ 0 1.0697 H CH₃ CH₂OCH₂Ph H H CH₂CH₂ 0 1.0698 H CH₃ CH₂OCH₂CH₂OH H F CH₂CH₂ 0 1.0699 H CH₃ CH₂OCH₂CH₂OH H Cl CH₂CH₂ 0 1.0700 H CH₃ CH₂OCH₂CH₂OH H H CH₂CH₂ 0 1.0701 H CH₃ CH₂OCH₂CH₂Cl H F CH₂CH₂ 0 1.0702 H CH₃ CH₂OCH₂CH₂Cl H Cl CH₂CH₂ 0 1.0703 H CH₃ CH₂OCH₂CH₂Cl H H CH₂CH₂ 0 1.0704 H CH₃ CH₂OCH₂CF₃ H F CH₂CH₂ 0 1.0705 H CH₃ CH₂OCH₂CF₃ H Cl CH₂CH₂ 0 1.0706 H CH₃ CH₂OCH₂CF₃ H H CH₂CH₂ 0 1.0707 H CH₃ CH₂OCH₂CH═CH₂ H F CH₂CH₂ 0 1.0708 H CH₃ CH₂OCH₂CH═CH₂ H Cl CH₂CH₂ 0 1.0709 H CH₃ CH₂OCH₂CH═CH₂ H H CH₂CH₂ 0 1.0710 H CH₃ CH₂O(CO)CH₃ H F CH₂CH₂ 0 1.0711 H CH₃ CH₂O(CO)CH₃ H Cl CH₂CH₂ 0 1.0712 H CH₃ CH₂O(CO)CH₃ H H CH₂CH₂ 0 1.0713 H CH₃ CH₂OCH₂C≡CH H F CH₂CH₂ 0 1.0714 H CH₃ CH₂OCH₂C≡CH H Cl CH₂CH₂ 0 1.0715 H CH₃ CH₂OCH₂C≡CH H H CH₂CH₂ 0 1.0716 H CH₃ CH₂OCH₂C≡CCH₃ H F CH₂CH₂ 0 1.0717 H CH₃ CH₂OCH₂C≡CCH₃ H Cl CH₂CH₂ 0 1.0718 H CH₃ CH₂OCH₂C≡CCH₃ H H CH₂CH₂ 0 1.0719 H CH₃

H F CH₂CH₂ 0 1.0720 H CH₃

H Cl CH₂CH₂ 0 1.0721 H CH₃

H H CH₂CH₂ 0 1.0722 H CH₃

H F CH₂CH₂ 0 1.0723 H CH₃

H Cl CH₂CH₂ 0 1.0724 H CH₃

H H CH₂CH₂ 0 1.0725 H CH₃

H F CH₂CH₂ 0 1.0726 H CH₃

H Cl CH₂CH₂ 0 1.0727 H CH₃

H H CH₂CH₂ 0 1.0728 H CH₃

H F CH₂CH₂ 0 1.0729 H CH₃

H Cl CH₂CH₂ 0 1.0730 H CH₃

H H CH₂CH₂ Q 1.0731 H CH₃

H F CH₂CH₂ 0 1.0732 H CH₃

H Cl CH₂CH₂ 0 1.0733 H CH₃

H H CH₂CH₂ 0 1.0734 H CH₃

H F CH₂CH₂ 0 1.0735 H CH₃

H Cl CH₂CH₂ 0 1.0736 H CH₃

H H CH₂CH₂ 0 1.0737 H CH₃ CH₂OCH₂CH₂OCH₃ H F CH₂CH₂ 1 1.0738 H CH₃ CH₂OCH₂CH₂OCH₃ H H CH₂CH₂ 1 1.0739 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ H F CH₂CH₂ 1 1.0740 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ H H CH₂CH₂ 1 1.0741 H CH₃ CH₂OCH₂CH₂OCH₃ H Cl CH₂CH₂ 1 1.0742 H H CH₂OCH₂CH₂OCH₃ H F NC(O)C(CH₃)₃ 0 1.0743 H H CH₂OCH₂CH₂OCH₃ H Cl NC(O)C(CH₃)₃ 0 1.0744 H H CH₂OCH₂CH₂OCH₃ H H NC(O)C(CH₃)₃ 0 1.0745 H H CH₂OCH₂CH₂OCH₂CH₃ H F NC(O)C(CH₃)₃ 0 1.0746 H H CH₂OCH₂CH₂OCH₂CH₃ H Cl NC(O)C(CH₃)₃ 0 1.0747 H H CH₂OCH₂CH₂OCH₂CH₃ H H NC(O)C(CH₃)₃ 0 1.0748 H H CH₂N(CH₃)SO₂CH₃ H F NC(O)C(CH₃)₃ 0 1.0749 H H CH₂N(CH₃)SO₂CH₃ H Cl NC(O)C(CH₃)₃ 0 1.0750 H H CH₂N(CH₃)SO₂CH₃ H H NC(O)C(CH₃)₃ 0 1.0751 H H CH₂OCH₂Ph H F NC(O)C(CH₃)₃ 0 1.0752 H H CH₂OCH₂Ph H Cl NC(O)C(CH₃)₃ 0 1.0753 H H CH₂OCH₂Ph H H NC(O)C(CH₃)₃ 0 1.0754 H H CH₂OCH₂CH₂OH H F NC(O)C(CH₃)₃ 0 1.0755 H H CH₂OCH₂CH₂OH H Cl NC(O)C(CH₃)₃ 0 1.0756 H H CH₂OCH₂CH₂OH H H NC(O)C(CH₃)₃ 0 1.0757 H H CH₂OCH₂CH₂Cl H F NO(O)O(CH₃)₃ 0 1.0758 H H CH₂OCH₂CH₂Cl H Cl NC(O)C(CH₃)₃ 0 1.0759 H H CH₂OCH₂CH₂Cl H H NO(O)C(CH₃)₃ 0 1.0760 H H CH₂OCH₂CF₃ H F NC(O)C(CH₃)₃ 0 1.0761 H H CH₂OCH₂CF₃ H Cl NC(O)C(CH₃)₃ 0 1.0762 H H CH₂OCH₂CF₃ H H NC(O)C(CH₃)₃ 0 1.0763 H H CH₂OCH₂CH═CH₂ H F NC(O)C(CH₃)₃ 0 1.0764 H H CH₂OCH₂CH═CH₂ H Cl NC(O)C(CH₃)₃ 0 1.0765 H H CH₂OCH₂CH═CH₂ H H NC(O)C(CH₃)₃ 0 1.0766 H H CH₂O(CO)CH₃ H F NC(O)C(CH₃)₃ 0 1.0767 H H CH₂O(CO)CH₃ H Cl NC(O)C(CH₃)₃ 0 1.0768 H H CH₂O(CO)CH₃ H H NC(O)C(CH₃)₃ 0 1.0769 H H CH₂OCH₂C≡CH H F NC(O)C(CH₃)₃ 0 1.0770 H H CH₂OCH₂C≡CH H Cl NC(O)C(CH₃)₃ 0 1.0771 H H CH₂OCH₂C≡CH H H NC(O)C(CH₃)₃ 0 1.0772 H H CH₂OCH₂C≡CCH₃ H F NC(O)C(CH₃)₃ 0 1.0773 H H CH₂OCH₂C≡CCH₃ H Cl NC(O)C(CH₃)₃ 0 1.0774 H H CH₂OCH₂C≡CCH₃ H H NC(O)C(CH₃)₃ 0 1.0775 H H

H F NC(O)C(CH₃)₃ 0 1.0776 H H

H Cl NC(O)C(CH₃)₃ 0 1.0777 H H

H H NC(O)C(CH₃)₃ 0 1.0778 H H

H F NC(O)C(CH₃)₃ 0 1.0779 H H

H Cl NC(O)C(CH₃)₃ 0 1.0780 H H

H H NC(O)C(CH₃)₃ 0 1.0781 H H

H F NC(O)C(CH₃)₃ 0 1.0782 H H

H Cl NC(O)C(CH₃)₃ 0 1.0783 H H

H H NC(O)C(CH₃)₃ 0 1.0784 H H

H F NC(O)C(CH₃)₃ 0 1.0785 H H

H Cl NC(O)C(CH₃)₃ 0 1.0786 H H

H H NC(O)C(CH₃)₃ 0 1.0787 H H

H F NC(O)C(CH₃)₃ 0 1.0788 H H

H Cl NC(O)C(CH₃)₃ 0 1.0789 H H

H H NC(O)C(CH₃)₃ 0 1.0790 H H

H F NC(O)C(CH₃)₃ 0 1.0791 H H

H Cl NC(O)C(CH₃)₃ 0 1.0792 H H

H H NC(O)C(CH₃)₃ 0 1.0793 H H CH₂OCH₂CH₂OCH₃ H F NC(O)C(CH₃)₃ 1 1.0794 H H CH₂OCH₂CH₂OCH₃ H H NC(O)C(CH₃)₃ 1 1.0795 H H CH₂OCH₂CH₂OCH₂CH₃ H F NC(O)C(CH₃)₃ 1 1.0796 H H CH₂OCH₂CH₂OCH₂CH₃ H H NC(O)C(CH₃)₃ 1 1.0797 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H F NC(O)C(CH₃)₃ 0 1.0798 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H Cl NC(O)C(CH₃)₃ 0 1.0799 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H H NC(O)C(CH₃)₃ 0 1.0800 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ H F NC(O)C(CH₃)₃ 0 1.0801 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ H Cl NC(O)C(CH₃)₃ 0 1.0802 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ H H NC(O)C(CH₃)₃ 0 1.0803 CH₃ CH₃ CH₂N(CH₃)SO₂CH₃ H F NC(O)C(CH₃)₃ 0 1.0804 CH₃ CH₃ CH₂N(CH₃)SO₂CH₃ H Cl NC(O)C(CH₃)₃ 0 1.0805 CH₃ CH₃ CH₂N(CH₃)SO₂CH₃ H H NC(O)C(CH₃)₃ 0 1.0806 CH₃ CH₃ CH₂OCH₂Ph H F NC(O)C(CH₃)₃ 0 1.0807 CH₃ CH₃ CH₂OCH₂Ph H Cl NC(O)C(CH₃)₃ 0 1.0808 CH₃ CH₃ CH₂OCH₂Ph H H NC(O)C(CH₃)₃ 0 1.0809 CH₃ CH₃ CH₂OCH₂CH₂OH H F NC(O)C(CH₃)₃ 0 1.0810 CH₃ CH₃ CH₂OCH₂CH₂OH H Cl NC(O)C(CH₃)₃ 0 1.0811 CH₃ CH₃ CH₂OCH₂CH₂OH H H NC(O)C(CH₃)₃ 0 1.0812 CH₃ CH₃ CH₂OCH₂CH₂Cl H F NC(O)C(CH₃)₃ 0 1.0813 CH₃ CH₃ CH₂OCH₂CH₂Cl H Cl NC(O)C(CH₃)₃ 0 1.0814 CH₃ CH₃ CH₂OCH₂CH₂Cl H H NC(O)C(CH₃)₃ 0 1.0815 CH₃ CH₃ CH₂OCH₂CF₃ H F NC(O)C(CH₃)₃ 0 1.0816 CH₃ CH₃ CH₂OCH₂CF₃ H Cl NC(O)C(CH₃)₃ 0 1.0817 CH₃ CH₃ CH₂OCH₂CF₃ H H NC(O)C(CH₃)₃ 0 1.0818 CH₃ CH₃ CH₂OCH₂CH═CH₂ H F NC(O)C(CH₃)₃ 0 1.0819 CH₃ CH₃ CH₂OCH₂CH═CH₂ H Cl NC(O)C(CH₃)₃ 0 1.0820 CH₃ CH₃ CH₂OCH₂CH═CH₂ H H NC(O)C(CH₃)₃ 0 1.0821 CH₃ CH₃ CH₂O(CO)CH₃ H F NC(O)C(CH₃)₃ 0 1.0822 CH₃ CH₃ CH₂O(CO)CH₃ H Cl NC(O)C(CH₃)₃ 0 1.0823 CH₃ CH₃ CH₂O(CO)CH₃ H H NC(O)C(CH₃)₃ 0 1.0824 CH₃ CH₃ CH₂OCH₂C≡CH H F NC(O)C(CH₃)₃ 0 1.0825 CH₃ CH₃ CH₂OCH₂C≡CH H Cl NC(O)C(CH₃)₃ 0 1.0826 CH₃ CH₃ CH₂OCH₂C≡CH H H NC(O)C(CH₃)₃ 0 1.0827 CH₃ CH₃ CH₂OCH₂C≡CCH₃ H F NC(O)C(CH₃)₃ 0 1.0828 CH₃ CH₃ CH₂OCH₂C≡CCH₃ H Cl NC(O)C(CH₃)₃ 0 1.0829 CH₃ CH₃ CH₂OCH₂C≡CCH₃ H H NC(O)C(CH₃)₃ 0 1.0830 CH₃ CH₃

H F NC(O)C(CH₃)₃ 0 1.0831 CH₃ CH₃

H Cl NC(O)C(CH₃)₃ 0 1.0832 CH₃ CH₃

H H NC(O)C(CH₃)₃ 0 1.0833 CH₃ CH₃

H F NC(O)C(CH₃)₃ 0 1.0834 CH₃ CH₃

H Cl NC(O)C(CH₃)₃ 0 1.0835 CH₃ CH₃

H H NC(O)C(CH₃)₃ 0 1.0836 CH₃ CH₃

H F NC(O)C(CH₃)₃ 0 1.0837 CH₃ CH₃

H Cl NC(O)C(CH₃)₃ 0 1.0838 CH₃ CH₃

H H NC(O)C(CH₃)₃ 0 1.0839 CH₃ CH₃

H F NC(O)C(CH₃)₃ 0 1.0840 CH₃ CH₃

H Cl NC(O)C(CH₃)₃ 0 1.0841 CH₃ CH₃

H H NC(O)C(CH₃)₃ 0 1.0842 CH₃ CH₃

H F NC(O)C(CH₃)₃ 0 1.0843 CH₃ CH₃

H Cl NC(O)C(CH₃)₃ 0 1.0844 CH₃ CH₃

H H NC(O)C(CH₃)₃ 0 1.0845 CH₃ CH₃

H F NC(O)C(CH₃)₃ 0 1.0846 CH₃ CH₃

H Cl NC(O)C(CH₃)₃ 0 1.0847 CH₃ CH₃

H H NC(O)C(CH₃)₃ 0 1.0848 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H F NC(O)C(CH₃)₃ 1 1.0849 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H H NC(O)C(CH₃)₃ 1 1.0850 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ H F NC(O)C(CH₃)₃ 1 1.0851 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ H H NC(O)C(CH₃)₃ 1 1.0852 H CH₃ CH₂OCH₂CH₂OCH₃ H F NC(O)C(CH₃)₃ 0 1.0853 H CH₃ CH₂OCH₂CH₂OCH₃ H Cl NC(O)C(CH₃)₃ 0 1.0854 H CH₃ CH₂OCH₂CH₂OCH₃ H H NC(O)C(CH₃)₃ 0 1.0855 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ H F NC(O)C(CH₃)₃ 0 1.0856 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ H Cl NC(O)C(CH₃)₃ 0 1.0857 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ H H NC(O)C(CH₃)₃ 0 1.0858 H CH₃ CH₂N(CH₃)SO₂CH₃ H F NC(O)C(CH₃)₃ 0 1.0859 H CH₃ CH₂N(CH₃)SO₂CH₃ H Cl NC(O)C(CH₃)₃ 0 1.0860 H CH₃ CH₂N(CH₃)SO₂CH₃ H H NC(O)C(CH₃)₃ 0 1.0861 H CH₃ CH₂OCH₂Ph H F NC(O)C(CH₃)₃ 0 1.0862 H CH₃ CH₂OCH₂Ph H Cl NC(O)C(CH₃)₃ 0 1.0863 H CH₃ CH₂OCH₂Ph H H NC(O)C(CH₃)₃ 0 1.0864 H CH₃ CH₂OCH₂CH₂OH H F NC(O)C(CH₃)₃ 0 1.0865 H CH₃ CH₂OCH₂CH₂OH H Cl NC(O)C(CH₃)₃ 0 1.0866 H CH₃ CH₂OCH₂CH₂OH H H NC(O)C(CH₃)₃ 0 1.0867 H CH₃ CH₂OCH₂CH₂Cl H F NC(O)C(CH₃)₃ 0 1.0868 H CH₃ CH₂OCH₂CH₂Cl H Cl NC(O)C(CH₃)₃ 0 1.0869 H CH₃ CH₂OCH₂CH₂Cl H H NC(O)C(CH₃)₃ 0 1.0870 H CH₃ CH₂OCH₂CF₃ H F NC(O)C(CH₃)₃ 0 1.0871 H CH₃ CH₂OCH₂CF₃ H Cl NC(O)C(CH₃)₃ 0 1.0872 H CH₃ CH₂OCH₂CF₃ H H NC(O)C(CH₃)₃ 0 1.0873 H CH₃ CH₂OCH₂CH═CH₂ H F NC(O)C(CH₃)₃ 0 1.0874 H CH₃ CH₂OCH₂CH═CH₂ H Cl NC(O)C(CH₃)₃ 0 1.0875 H CH₃ CH₂OCH₂CH═CH₂ H H NC(O)C(CH₃)₃ 0 1.0876 H CH₃ CH₂O(CO)CH₃ H F NC(O)C(CH₃)₃ 0 1.0877 H CH₃ CH₂O(CO)CH₃ H Cl NC(O)C(CH₃)₃ 0 1.0878 H CH₃ CH₂O(CO)CH₃ H H NC(O)C(CH₃)₃ 0 1.0879 H CH₃ CH₂OCH₂C≡CH H F NC(O)C(CH₃)₃ 0 1.0880 H CH₃ CH₂OCH₂C≡CH H Cl NC(O)C(CH₃)₃ 0 1.0881 H CH₃ CH₂OCH₂C≡CH H H NC(O)C(CH₃)₃ 0 1.0882 H CH₃ CH₂OCH₂C≡CCH₃ H F NC(O)C(CH₃₎ ₃ 0 1.0883 H CH₃ CH₂OCH₂C≡CCH₃ H Cl NC(O)C(CH₃)₃ 0 1.0884 H CH₃ CH₂OCH₂C≡CCH₃ H H NC(O)C(CH₃)₃ 0 1.0885 H CH₃

H F NC(O)C(CH₃)₃ 0 1.0886 H CH₃

H Cl NC(O)C(CH₃)₃ 0 1.0887 H CH₃

H H NC(O)C(CH₃)₃ 0 1.0888 H CH₃

H F NC(O)C(CH₃)₃ 0 1.0889 H CH₃

H Cl NC(O)C(CH₃)₃ 0 1.0890 H CH₃

H H NC(O)C(CH₃)₃ 0 1.0891 H CH₃

H F NC(O)C(CH₃)₃ 0 1.0892 H CH₃

H Cl NC(O)C(CH₃)₃ 0 1.0893 H CH₃

H H NC(O)C(CH₃)₃ 0 1.0894 H CH₃

H F NC(O)C(CH₃)₃ 0 1.0895 H CH₃

H Cl NC(O)C(CH₃)₃ 0 1.0896 H CH₃

H H NC(O)C(CH₃)₃ 0 1.0897 H CH₃

H F NC(O)C(CH₃)₃ 0 1.0898 H CH₃

H Cl NC(O)C(CH₃)₃ 0 1.0899 H CH₃

H H NC(O)C(CH₃)₃ 0 1.0900 H CH₃

H F NC(O)C(CH₃)₃ 0 1.0901 H CH₃

H Cl NC(O)C(CH₃)₃ 0 1.0902 H CH₃

H H NC(O)C(CH₃)₃ 0 1.0903 H CH₃ CH₂OCH₂CH₂OCH₃ H F NC(O)C(CH₃)₃ 1 1.0904 H CH₃ CH₂OCH₂CH₂OCH₃ H H NC(O)C(CH₃)₃ 1 1.0905 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ H F NC(O)C(CH₃)₃ 1 1.0906 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ H H NC(O)C(CH₃)₃ 1 1.0907 H H CH₃ H F NSO₂N(CH₃)₂ 0 1.0908 H H CH₃ H Cl NSO₂N(CH₃)₂ 0 1.0909 H H CH₃ H H NSO₂N(CH₃)₂ 0 1.0910 H H CH₃ CH₃ F NSO₂N(CH₃)₂ 0 1.0911 H H CH₃ CH₃ Cl NSO₂N(CH₃)₂ 0 1.0912 H H CH₃ CH₃ H NSO₂N(CH₃)₂ 0 1.0913 H H CH₂CH₃ H F NSO₂N(CH₃)₂ 0 1.0914 H H CH₂CH₃ H Cl NSO₂N(CH₃)₂ 0 1.0915 H H CH₂CH₃ H H NSO₂N(CH₃)₂ 0 1.0916 H H CH₂CH₂CH₃ H F NSO₂N(CH₃)₂ 0 1.0917 H H CH₂CH₂CH₃ H Cl NSO₂N(CH₃)₂ 0 1.0918 H H CH₂CH₂CH₃ H H NSO₂N(CH₃)₂ 0 1.0919 H H CH₂OCH₃ H F NSO₂N(CH₃)₂ 0 1.0920 H H CH₂OCH₃ H Cl NSO₂N(CH₃)₂ 0 1.0921 H H CH₂OCH₃ H H NSO₂N(CH₃)₂ 0 1.0922 H H CH₂OCH₂CH₃ H F NSO₂N(CH₃)₂ 0 1.0923 H H CH₂OCH₂CH₃ H Cl NSO₂N(CH₃)₂ 0 1.0924 H H CH₂OCH₂CH₃ H H NSO₂N(CH₃)₂ 0 1.0925 H H CH₂OCH₂CH₂OCH₃ H F NSO₂N(CH₃)₂ 0 1.0926 H H CH₂OCH₂CH₂OCH₃ H Cl NSO₂N(CH₃)₂ 0 1.0927 H H CH₂OCH₂CH₂OCH₃ H H NSO₂N(CH₃)₂ 0 1.0928 H H CH₂OCH₂CH₂OCH₂CH₃ H F NSO₂N(CH₃)₂ 0 1.0929 H H CH₂OCH₂CH₂OCH₂CH₃ H Cl NSO₂N(CH₃)₂ 0 1.0930 H H CH₂OCH₂CH₂OCH₂CH₃ H H NSO₂N(CH₃)₂ 0 1.0931 H H CH₂CH₂OCH₃ H F NSO₂N(CH₃)₂ 0 1.0932 H H CH₂CH₂OCH₃ H Cl NSO₂N(CH₃)₂ 0 1.0933 H H CH₂CH₂OCH₃ H H NSO₂N(CH₃)₂ 0 1.0934 H H CH₂OCH₂C≡CH H F NSO₂N(CH₃)₂ 0 1.0935 H H CH₂OCH₂C≡CH H Cl NSO₂N(CH₃)₂ 0 1.0936 H H CH₂OCH₂C≡CH H H NSO₂N(CH₃)₂ 0 1.0937 H H CH₂OCH₂C≡CCH₃ H F NSO₂N(CH₃)₂ 0 1.0938 H H CH₂OCH₂C≡CCH₃ H Cl NSO₂N(CH₃)₂ 0 1.0939 H H CH₂OCH₂C≡CCH₃ H H NSO₂N(CH₃)₂ 0 1.0940 H H CH₂CH₂CH₂OCH₃ H F NSO₂N(CH₃)₂ 0 1.0941 H H CH₂CH₂CH₂OCH₃ H Cl NSO₂N(CH₃)₂ 0 1.0942 H H CH₂CH₂CH₂OCH₃ H H NSO₂N(CH₃)₂ 0 1.0943 H H CH₂OCH₂OCH₃ H F NSO₂N(CH₃)₂ 0 1.0944 H H CH₂OCH₂OCH₃ H Cl NSO₂N(CH₃)₂ 0 1.0945 H H CH₂OCH₂OCH₃ H H NSO₂N(CH₃)₂ 0 1.0946 H H CH₂N(CH₃)SO₂CH₃ H F NSO₂N(CH₃)₂ 0 1.0947 H H CH₂N(CH₃)SO₂CH₃ H Cl NSO₂N(CH₃)₂ 0 1.0948 H H CH₂N(CH₃)SO₂CH₃ H H NSO₂N(CH₃)₂ 0 1.0949 H H CF₃ H F NSO₂N(CH₃)₂ 0 1.0950 H H CF₃ H Cl NSO₂N(CH₃)₂ 0 1.0951 H H CF₃ H H NSO₂N(CH₃)₂ 0 1.0952 H H CH₂OCH₂CF₃ H F NSO₂N(CH₃)₂ 0 1.0953 H H CH₂OCH₂CF₃ H Cl NSO₂N(CH₃)₂ 0 1.0954 H H CH₂OCH₂CF₃ H H NSO₂N(CH₃)₂ 0 1.0955 H H CH₂OCH₂Ph H F NSO₂N(CH₃)₂ 0 1.0956 H H CH₂OCH₂Ph H Cl NSO₂N(CH₃)₂ 0 1.0957 H H CH₂OCH₂Ph H H NSO₂N(CH₃)₂ 0 1.0958 H H CH₂OCH₂CH═CH₂ H F NSO₂N(CH₃)₂ 0 1.0959 H H CH₂OCH₂CH═CH₂ H Cl NSO₂N(CH₃)₂ 0 1.0960 H H CH₂OCH₂CH═CH₂ H H NSO₂N(CH₃)₂ 0 1.0961 H H

H F NSO₂N(CH₃)₂ 0 1.0962 H H

H Cl NSO₂N(CH₃)₂ 0 1.0963 H H

H H NSO₂N(CH₃)₂ 0 1.0964 H H

H F NSO₂N(CH₃)₂ 0 1.0965 H H

H Cl NSO₂N(CH₃)₂ 0 1.0966 H H

H H NSO₂N(CH₃)₂ 0 1.0967 H H

H F NSO₂N(CH₃)₂ 0 1.0968 H H

H Cl NSO₂N(CH₃)₂ 0 1.0969 H H

H H NSO₂N(CH₃)₂ 0 1.0970 H H

H F NSO₂N(CH₃)₂ 0 1.0971 H H

H Cl NSO₂N(CH₃)₂ 0 1.0972 H H

H H NSO₂N(CH₃)₂ 0 1.0973 H H

H F NSO₂N(CH₃)₂ 0 1.0974 H H

H Cl NSO₂N(CH₃)₂ 0 1.0975 H H

H H NSO₂N(CH₃)₂ 0 1.0976 H H

H F NSO₂N(CH₃)₂ 0 1.0977 H H

H Cl NSO₂N(CH₃)₂ 0 1.0978 H H

H H NSO₂N(CH₃)₂ 0 1.0979 H H CH₃ H F NSO₂N(CH₃)₂ 1 1.0980 H H CH₂OCH₃ H F NSO₂N(CH₃)₂ 1 1.0981 H H CH₂OCH₂CH₂OCH₃ H F NSO₂N(CH₃)₂ 1 1.0982 H H CH₂CH₂CH₂OCH₃ H F NSO₂N(CH₃)₂ 1 1.0983 H H CH₂CH₃ H F NSO₂N(CH₃)₂ 1 1.0984 H H CH₃ H H NSO₂N(CH₃)₂ 1 1.0985 H H CH₂OCH₃ H H NSO₂N(CH₃)₂ 1 1.0986 H H CH₂OCH₂CH₂OCH₃ H H NSO₂N(CH₃)₂ 1 1.0987 H H CH₂CH₂CH₂OCH₃ H H NSO₂N(CH₃)₂ 1 1.0988 H H CH₂CH₃ H H NSO₂N(CH₃)₂ 1 1.0989 CH₃ CH₃ CH₃ H F NSO₂N(CH₃)₂ 0 1.0990 CH₃ CH₃ CH₃ H Cl NSO₂N(CH₃)₂ 0 1.0991 CH₃ CH₃ CH₃ H H NSO₂N(CH₃)₂ 0 1.0992 CH₃ CH₃ CH₃ CH₃ F NSO₂N(CH₃)₂ 0 1.0993 CH₃ CH₃ CH₃ CH₃ Cl NSO₂N(CH₃)₂ 0 1.0994 CH₃ CH₃ CH₃ CH₃ H NSO₂N(CH₃)₂ 0 1.0995 CH₃ CH₃ CH₂CH₃ H F NSO₂N(CH₃)₂ 0 1.0996 CH₃ CH₃ CH₂CH₃ H Cl NSO₂N(CH₃)₂ 0 1.0997 CH₃ CH₃ CH₂CH₃ H H NSO₂N(CH₃)₂ 0 1.0998 CH₃ CH₃ CH₂CH₂CH₃ H F NSO₂N(CH₃)₂ 0 1.0999 CH₃ CH₃ CH₂CH₂CH₃ H Cl NSO₂N(CH₃)₂ 0 1.1000 CH₃ CH₃ CH₂CH₂CH₃ H H NSO₂N(CH₃)₂ 0 1.1001 CH₃ CH₃ CH₂OCH₃ H F NSO₂N(CH₃)₂ 0 1.1002 CH₃ CH₃ CH₂OCH₃ H Cl NSO₂N(CH₃)₂ 0 1.1003 CH₃ CH₃ CH₂OCH₃ H H NSO₂N(CH₃)₂ 0 1.1004 CH₃ CH₃ CH₂OCH₂CH₃ H F NSO₂N(CH₃)₂ 0 1.1005 CH₃ CH₃ CH₂OCH₂CH₃ H Cl NSO₂N(CH₃)₂ 0 1.1006 CH₃ CH₃ CH₂OCH₂CH₃ H H NSO₂N(CH₃)₂ 0 1.1007 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H F NSO₂N(CH₃)₂ 0 1.1008 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H Cl NSO₂N(CH₃)₂ 0 1.1009 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H H NSO₂N(CH₃)₂ 0 1.1010 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ H F NSO₂N(CH₃)₂ 0 1.1011 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ H Cl NSO₂N(CH₃)₂ 0 1.1012 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ H H NSO₂N(CH₃)₂ 0 1.1013 CH₃ CH₃ CH₂CH₂OCH₃ H F NSO₂N(CH₃)₂ 0 1.1014 CH₃ CH₃ CH₂CH₂OCH₃ H Cl NSO₂N(CH₃)₂ 0 1.1015 CH₃ CH₃ CH₂CH₂OCH₃ H H NSO₂N(CH₃)₂ 0 1.1016 CH₃ CH₃ CH₂OCH₂C≡CH H F NSO₂N(CH₃)₂ 0 1.1017 CH₃ CH₃ CH₂OCH₂C≡CH H Cl NSO₂N(CH₃)₂ 0 1.1018 CH₃ CH₃ CH₂OCH₂C≡CH H H NSO₂N(CH₃)₂ 0 1.1019 CH₃ CH₃ CH₂OCH₂C≡CCH₃ H F NSO₂N(CH₃)₂ 0 1.1020 CH₃ CH₃ CH₂OCH₂C≡CCH₃ H Cl NSO₂N(CH₃)₂ 0 1.1021 CH₃ CH₃ CH₂OCH₂C≡CCH₃ H H NSO₂N(CH₃)₂ 0 1.1022 CH₃ CH₃ CH₂CH₂CH₂OCH₃ H F NSO₂N(CH₃)₂ 0 1.1023 CH₃ CH₃ CH₂CH₂CH₂OCH₃ H Cl NSO₂N(CH₃)₂ 0 1.1024 CH₃ CH₃ CH₂CH₂CH₂OCH₃ H H NSO₂N(CH₃)₂ 0 1.1025 CH₃ CH₃ CH₂OCH₂OCH₃ H F NSO₂N(CH₃)₂ 0 1.1026 CH₃ CH₃ CH₂OCH₂OCH₃ H Cl NSO₂N(CH₃)₂ 0 1.1027 CH₃ CH₃ CH₂OCH₂OCH₃ H H NSO₂N(CH₃)₂ 0 1.1028 CH₃ CH₃ CH₂N(CH₃)SO₂CH₃ H F NSO₂N(CH₃)₂ 0 1.1029 CH₃ CH₃ CH₂N(CH₃)SO₂CH₃ H Cl NSO₂N(CH₃)₂ 0 1.1030 CH₃ CH₃ CH₂N(CH₃)SO₂CH₃ H H NSO₂N(CH₃)₂ 0 1.1031 CH₃ CH₃ CF₃ H F NSO₂N(CH₃)₂ 0 1.1032 CH₃ CH₃ CF₃ H Cl NSO₂N(CH₃)₂ 0 1.1033 CH₃ CH₃ CF₃ H H NSO₂N(CH₃)₂ 0 1.1034 CH₃ CH₃ CH₂OCH₂CF₃ H F NSO₂N(CH₃)₂ 0 1.1035 CH₃ CH₃ CH₂OCH₂CF₃ H Cl NSO₂N(CH₃)₂ 0 1.1036 CH₃ CH₃ CH₂OCH₂CF₃ H H NSO₂N(CH₃)₂ 0 1.1037 CH₃ CH₃ CH₂OCH₂Ph H F NSO₂N(CH₃)₂ 0 1.1038 CH₃ CH₃ CH₂OCH₂Ph H Cl NSO₂N(CH₃)₂ 0 1.1039 CH₃ CH₃ CH₂OCH₂Ph H H NSO₂N(CH₃)₂ 0 1.1040 CH₃ CH₃ CH₂OCH₂CH═CH₂ H F NSO₂N(CH₃)₂ 0 1.1041 CH₃ CH₃ CH₂OCH₂CH═CH₂ H Cl NSO₂N(CH₃)₂ 0 1.1042 CH₃ CH₃ CH₂OCH₂CH═CH₂ H H NSO₂N(CH₃)₂ 0 1.1043 CH₃ CH₃

H F NSO₂N(CH₃)₂ 0 1.1044 CH₃ CH₃

H Cl NSO₂N(CH₃)₂ 0 1.1045 CH₃ CH₃

H H NSO₂N(CH₃)₂ 0 1.1046 CH₃ CH₃

H F NSO₂N(CH₃)₂ 0 1.1047 CH₃ CH₃

H Cl NSO₂N(CH₃)₂ 0 1.1048 CH₃ CH₃

H H NSO₂N(CH₃)₂ 0 1.1049 CH₃ CH₃

H F NSO₂N(CH₃)₂ 0 1.1050 CH₃ CH₃

H Cl NSO₂N(CH₃)₂ 0 1.1051 CH₃ CH₃

H H NSO₂N(CH₃)₂ 0 1.1052 CH₃ CH₃

H F NSO₂N(CH₃)₂ 0 1.1053 CH₃ CH₃

H Cl NSO₂N(CH₃)₂ 0 1.1054 CH₃ CH₃

H H NSO₂N(CH₃)₂ 0 1.1055 CH₃ CH₃

H F NSO₂N(CH₃)₂ 0 1.1056 CH₃ CH₃

H Cl NSO₂N(CH₃)₂ 0 1.1057 CH₃ CH₃

H H NSO₂N(CH₃)₂ 0 1.1058 CH₃ CH₃

H F NSO₂N(CH₃)₂ 0 1.1059 CH₃ CH₃

H Cl NSO₂N(CH₃)₂ 0 1.1060 CH₃ CH₃

H H NSO₂N(CH₃)₂ 0 1.1061 CH₃ CH₃ CH₃ H F NSO₂N(CH₃)₂ 1 1.1062 CH₃ CH₃ CH₂OCH₃ H F NSO₂N(CH₃)₂ 1 1.1063 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H F NSO₂N(CH₃)₂ 1 1.1064 CH₃ CH₃ CH₂CH₂CH₂OCH₃ H F NSO₂N(CH₃)₂ 1 1.1065 CH₃ CH₃ CH₂CH₃ H F NSO₂N(CH₃)₂ 1 1.1066 CH₃ CH₃ CH₃ H H NSO₂N(CH₃)₂ 1 1.1067 CH₃ CH₃ CH₂OCH₃ H H NSO₂N(CH₃)₂ 1 1.1068 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H H NSO₂N(CH₃)₂ 1 1.1069 CH₃ CH₃ CH₂CH₂CH₂OCH₃ H H NSO₂N(CH₃)₂ 1 1.1070 CH₃ CH₃ CH₂CH₃ H H NSO₂N(CH₃)₂ 1 1.1071 H CH₃ CH₃ H F NSO₂N(CH₃)₂ 0 1.1072 H CH₃ CH₃ H Cl NSO₂N(CH₃)₂ 0 1.1073 H CH₃ CH₃ H H NSO₂N(CH₃)₂ 0 1.1074 H CH₃ CH₃ CH₃ F NSO₂N(CH₃)₂ 0 1.1075 H CH₃ CH₃ CH₃ Cl NSO₂N(CH₃)₂ 0 1.1076 H CH₃ CH₃ CH₃ H NSO₂N(CH₃)₂ 0 1.1077 H CH₃ CH₂CH₃ H F NSO₂N(CH₃)₂ 0 1.1078 H CH₃ CH₂CH₃ H Cl NSO₂N(CH₃)₂ 0 1.1079 H CH₃ CH₂CH₃ H H NSO₂N(CH₃)₂ 0 1.1080 H CH₃ CH₂CH₂CH₃ H F NSO₂N(CH₃)₂ 0 1.1081 H CH₃ CH₂CH₂CH₃ H Cl NSO₂N(CH₃)₂ 0 1.1082 H CH₃ CH₂CH₂CH₃ H H NSO₂N(CH₃)₂ 0 1.1083 H CH₃ CH₂OCH₃ H F NSO₂N(CH₃)₂ 0 1.1084 H CH₃ CH₂OCH₃ H Cl NSO₂N(CH₃)₂ 0 1.1085 H CH₃ CH₂OCH₃ H H NSO₂N(CH₃)₂ 0 1.1086 H CH₃ CH₂OCH₂CH₃ H F NSO₂N(CH₃)₂ 0 1.1087 H CH₃ CH₂OCH₂CH₃ H Cl NSO₂N(CH₃)₂ 0 1.1088 H CH₃ CH₂OCH₂CH₃ H H NSO₂N(CH₃)₂ 0 1.1089 H CH₃ CH₂OCH₂CH₂OCH₃ H F NSO₂N(CH₃)₂ 0 1.1090 H CH₃ CH₂OCH₂CH₂OCH₃ H Cl NSO₂N(CH₃)₂ 0 1.1091 H CH₃ CH₂OCH₂CH₂OCH₃ H H NSO₂N(CH₃)₂ 0 1.1092 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ H F NSO₂N(CH₃)₂ 0 1.1093 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ H Cl NSO₂N(CH₃)₂ 0 1.1094 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ H H NSO₂N(CH₃)₂ 0 1.1095 H CH₃ CH₂CH₂OCH₃ H F NSO₂N(CH₃)₂ 0 1.1096 H CH₃ CH₂CH₂OCH₃ H Cl NSO₂N(CH₃)₂ 0 1.1097 H CH₃ CH₂CH₂OCH₃ H H NSO₂N(CH₃)₂ 0 1.1098 H CH₃ CH₂OCH₂C≡CH H F NSO₂N(CH₃)₂ 0 1.1099 H CH₃ CH₂OCH₂C≡CH H Cl NSO₂N(CH₃)₂ 0 1.1100 H CH₃ CH₂OCH₂C≡CH H H NSO₂N(CH₃)₂ 0 1.1101 H CH₃ CH₂OCH₂C≡CCH₃ H F NSO₂N(CH₃)₂ 0 1.1102 H CH₃ CH₂OCH₂C≡CCH₃ H Cl NSO₂N(CH₃)₂ 0 1.1103 H CH₃ CH₂OCH₂C≡CCH₃ H H NSO₂N(CH₃)₂ 0 1.1104 H CH₃ CH₂CH₂CH₂OCH₃ H F NSO₂N(CH₃)₂ 0 1.1105 H CH₃ CH₂CH₂CH₂OCH₃ H Cl NSO₂N(CH₃)₂ 0 1.1106 H CH₃ CH₂CH₂CH₂OCH₃ H H NSO₂N(CH₃)₂ 0 1.1107 H CH₃ CH₂OCH₂OCH₃ H F NSO₂N(CH₃)₂ 0 1.1108 H CH₃ CH₂OCH₂OCH₃ H Cl NSO₂N(CH₃)₂ 0 1.1109 H CH₃ CH₂OCH₂OCH₃ H H NSO₂N(CH₃)₂ 0 1.1110 H CH₃ CH₂N(CH₃)SO₂CH₃ H F NSO₂N(CH₃)₂ 0 1.1111 H CH₃ CH₂N(CH₃)SO₂CH₃ H Cl NSO₂N(CH₃)₂ 0 1.1112 H CH₃ CH₂N(CH₃)SO₂CH₃ H H NSO₂N(CH₃)₂ 0 1.1113 H CH₃ CF₃ H F NSO₂N(CH₃)₂ 0 1.1114 H CH₃ CF₃ H Cl NSO₂N(CH₃)₂ 0 1.1115 H CH₃ CF₃ H H NSO₂N(CH₃)₂ 0 1.1116 H CH₃ CH₂OCH₂CF₃ H F NSO₂N(CH₃)₂ 0 1.1117 H CH₃ CH₂OCH₂CF₃ H Cl NSO₂N(CH₃)₂ 0 1.1118 H CH₃ CH₂OCH₂CF₃ H H NSO₂N(CH₃)₂ 0 1.1119 H CH₃ CH₂OCH₂Ph H F NSO₂N(CH₃)₂ 0 1.1120 H CH₃ CH₂OCH₂Ph H Cl NSO₂N(CH₃)₂ 0 1.1121 H CH₃ CH₂OCH₂Ph H H NSO₂N(CH₃)₂ 0 1.1122 H CH₃ CH₂OCH₂CH═CH₂ H F NSO₂N(CH₃)₂ 0 1.1123 H CH₃ CH₂OCH₂CH═CH₂ H Cl NSO₂N(CH₃)₂ 0 1.1124 H CH₃ CH₂OCH₂CH═CH₂ H H NSO₂N(CH₃)₂ 0 1.1125 H CH₃

H F NSO₂N(CH₃)₂ 0 1.1126 H CH₃

H Cl NSO₂N(CH₃)₂ 0 1.1127 H CH₃

H H NSO₂N(CH₃)₂ 0 1.1128 H CH₃

H F NSO₂N(CH₃)₂ 0 1.1129 H CH₃

H Cl NSO₂N(CH₃)₂ 0 1.1130 H CH₃

H H NSO₂N(CH₃)₂ 0 1.1131 H CH₃

H F NSO₂N(CH₃)₂ 0 1.1132 H CH₃

H Cl NSO₂N(CH₃)₂ 0 1.1133 H CH₃

H H NSO₂N(CH₃)₂ 0 1.1134 H CH₃

H F NSO₂N(CH₃)₂ 0 1.1135 H CH₃

H Cl NSO₂N(CH₃)₂ 0 1.1136 H CH₃

H H NSO₂N(CH₃)₂ 0 1.1137 H CH₃

H F NSO₂N(CH₃)₂ 0 1.1138 H CH₃

H Cl NSO₂N(CH₃)₂ 0 1.1139 H CH₃

H H NSO₂N(CH₃)₂ 0 1.1140 H CH₃

H F NSO₂N(CH₃)₂ 0 1.1141 H CH₃

H Cl NSO₂N(CH₃)₂ 0 1.1142 H CH₃

H H NSO₂N(CH₃)₂ 0 1.1143 H CH₃ CH₃ H F NSO₂N(CH₃)₂ 1 1.1144 H CH₃ CH₂OCH₃ H F NSO₂N(CH₃)₂ 1 1.1145 H CH₃ CH₂OCH₂CH₂OCH₃ H F NSO₂N(CH₃)₂ 1 1.1146 H CH₃ CH₂CH₂CH₂OCH₃ H F NSO₂N(CH₃)₂ 1 1.1147 H CH₃ CH₂CH₃ H F NSO₂N(CH₃)₂ 1 1.1148 H CH₃ CH₃ H H NSO₂N(CH₃)₂ 1 1.1149 H CH₃ CH₂OCH₃ H H NSO₂N(CH₃)₂ 1 1.1150 H CH₃ CH₂OCH₂CH₂OCH₃ H H NSO₂N(CH₃)₂ 1 1.1151 H CH₃ CH₂CH₂CH₂OCH₃ H H NSO₂N(CH₃)₂ 1 1.1152 H CH₃ CH₂CH₃ H H NSO₂N(CH₃)₂ 1 1.1153 H H CH₃ H F

0 ¹H NMR (300 MHz; CDCl₃) δ 16.58 (s, 1H); 7.55 (m, 2H); 6.48 (m, 1H); 6.40 (m, 1H); 2.94 (m, 1H): 2.72 (m, 1H); 2.50 (s, 3H); 0.90-0.65 (m, 4H). 1.1154 H H CH₃ H F C(═C(CH₃)₂) 0 ¹H NMR (300 MHz; CDCl₃) δ 16.25 (s, 1H); 7.56 (m, 2H); 6.52 (m, 1H); 6.45 (m, 1H); 4.20 (m, 1H); 3.98 (m, 1H); 2.45 (s, 3H); 1.80 (s, 3H); 1.71 (s, 3H). 1.1155 H H CH₃ H H CH₂CH(COOCH₃) 0 R₇ = Br; ¹H NMR (300 MHz; CDCl₃) i.a. δ 7.44 (d, 2H); 6.54 (t, 1H), 6.53 + 6.42 (2d, 1H); 3.71 + 3.58 (2s, 3H); 2.41 + 2.40 (2s, 3H); tautomeric mixture. 1.1156 H H CH₃ H H CH₂CH(COOCH₃) 0 R₇ = H; NEt₃ salt (Example P14)

TABLE 2 Compounds of formula Ic: (Ic)

No. R₁ R₂ Z₁ R₃₀ X Y Physical data 2.0000 H H CH₂OCH₂CH₂OCH₃ H F CH₂ 2.0001 H H CH₂OCH₂CH₂OCH₃ H Cl CH₂ 2.0002 H H CH₂OCH₂CH₂OCH₃ H H CH₂ 2.0003 H H CH₂OCH₂CH₂OCH₂CH₃ H F CH₂ 2.0004 H H CH₂OCH₂CH₂OCH₂CH₃ H Cl CH₂ 2.0005 H H CH₂OCH₂CH₂OCH₂CH₃ H H CH₂ 2.0006 H H CH₂N(CH₃)SO₂CH₃ H F CH₂ 2.0007 H H CH₂N(CH₃)SO₂CH₃ H Cl CH₂ 2.0008 H H CH₂N(CH₃)SO₂CH₃ H H CH₂ 2.0009 H H CH₂OCH₂Ph H F CH₂ 2.0010 H H CH₂OCH₂Ph H Cl CH₂ 2.0011 H H CH₂OCH₂Ph H H CH₂ 2.0012 H H CH₂OCH₂CH₂OH H F CH₂ 2.0013 H H CH₂OCH₂CH₂OH H Cl CH₂ 2.0014 H H CH₂OCH₂CH₂OH H H CH₂ 2.0015 H H CH₂OCH₂CH₂Cl H F CH₂ 2.0016 H H CH₂OCH₂CH₂Cl H Cl CH₂ 2.0017 H H CH₂OCH₂CH₂Cl H H CH₂ 2.0018 H H CH₂OCH₂CF₃ H F CH₂ 2.0019 H H CH₂OCH₂CF₃ H Cl CH₂ 2.0020 H H CH₂OCH₂CF₃ H H CH₂ 2.0021 H H CH₂OCH₂CH═CH₂ H F CH₂ 2.0022 H H CH₂OCH₂CH═CH₂ H Cl CH₂ 2.0023 H H CH₂OCH₂CH═CH₂ H H CH₂ 2.0024 H H CH₂O(CO)CH₃ H F CH₂ 2.0025 H H CH₂O(CO)CH₃ H Cl CH₂ 2.0026 H H CH₂O(CO)CH₃ H H CH₂ 2.0027 H H CH₂OCH₂C≡CH H F CH₂ 2.0028 H H CH₂OCH₂C≡CH H Cl CH₂ 2.0029 H H CH₂OCH₂C≡CH H H CH₂ 2.0030 H H CH₂OCH₂C≡CCH₃ H F CH₂ 2.0031 H H CH₂OCH₂C≡CCH₃ H Cl CH₂ 2.0032 H H CH₂OCH₂C≡CCH₃ H H CH₂ 2.0033 H H

H F CH₂ 2.0034 H H

H Cl CH₂ 2.0035 H H

H H CH₂ 2.0036 H H

H F CH₂ 2.0037 H H

H Cl CH₂ 2.0038 H H

H H CH₂ 2.0039 H H

H F CH₂ 2.0040 H H

H Cl CH₂ 2.0041 H H

H H CH₂ 2.0042 H H

H F CH₂ 2.0043 H H

H Cl CH₂ 2.0044 H H

H H CH₂ 2.0045 H H

H F CH₂ 2.0046 H H

H Cl CH₂ 2.0047 H H

H H CH₂ 2.0048 H H

H F CH₂ 2.0049 H H

H Cl CH₂ 2.0050 H H

H H CH₂ 2.0051 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H F CH₂ 2.0052 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H Cl CH₂ 2.0053 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H H CH₂ 2.0054 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ H F CH₂ 2.0055 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ H Cl CH₂ 2.0056 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ H H CH₂ 2.0057 CH₃ CH₃ CH₂N(CH₃)SO₂CH₃ H F CH₂ 2.0058 CH₃ CH₃ CH₂N(CH₃)SO₂CH₃ H Cl CH₂ 2.0059 CH₃ CH₃ CH₂N(CH₃)SO₂CH₃ H H CH₂ 2.0060 CH₃ CH₃ CH₂OCH₂Ph H F CH₂ 2.0061 CH₃ CH₃ CH₂OCH₂Ph H Cl CH₂ 2.0062 CH₃ CH₃ CH₂OCH₂Ph H H CH₂ 2.0063 CH₃ CH₃ CH₂OCH₂CH₂OH H F CH₂ 2.0064 CH₃ CH₃ CH₂OCH₂CH₂OH H Cl CH₂ 2.0065 CH₃ CH₃ CH₂OCH₂CH₂OH H H CH₂ 2.0066 CH₃ CH₃ CH₂OCH₂CH₂Cl H F CH₂ 2.0067 CH₃ CH₃ CH₂OCH₂CH₂Cl H Cl CH₂ 2.0068 CH₃ CH₃ CH₂OCH₂CH₂Cl H H CH₂ 2.0069 CH₃ CH₃ CH₂OCH₂CF₃ H F CH₂ 2.0070 CH₃ CH₃ CH₂OCH₂CF₃ H Cl CH₂ 2.0071 CH₃ CH₃ CH₂OCH₂CF₃ H H CH₂ 2.0072 CH₃ CH₃ CH₂OCH₂CH═CH₂ H F CH₂ 2.0073 CH₃ CH₃ CH₂OCH₂CH═CH₂ H Cl CH₂ 2.0074 CH₃ CH₃ CH₂OCH₂CH═CH₂ H H CH₂ 2.0075 CH₃ CH₃ CH₂O(CO)CH₃ H F CH₂ 2.0076 CH₃ CH₃ CH₂O(CO)CH₃ H Cl CH₂ 2.0077 CH₃ CH₃ CH₂O(CO)CH₃ H H CH₂ 2.0078 CH₃ CH₃ CH₂OCH₂C≡CH H F CH₂ 2.0079 CH₃ CH₃ CH₂OCH₂C≡CH H Cl CH₂ 2.0080 CH₃ CH₃ CH₂OCH₂C≡CH H H CH₂ 2.0081 CH₃ CH₃ CH₂OCH₂C≡CCH₃ H F CH₂ 2.0082 CH₃ CH₃ CH₂OCH₂C≡CCH₃ H Cl CH₂ 2.0083 CH₃ CH₃ CH₂OCH₂C≡CCH₃ H H CH₂ 2.0084 CH₃ CH₃

H F CH₂ 2.0085 CH₃ CH₃

H Cl CH₂ 2.0086 CH₃ CH₃

H H CH₂ 2.0087 CH₃ CH₃

H F CH₂ 2.0088 CH₃ CH₃

H Cl CH₂ 2.0089 CH₃ CH₃

H H CH₂ 2.0090 CH₃ CH₃

H F CH₂ 2.0091 CH₃ CH₃

H Cl CH₂ 2.0092 CH₃ CH₃

H H CH₂ 2.0093 CH₃ CH₃

H F CH₂ 2.0094 CH₃ CH₃

H Cl CH₂ 2.0095 CH₃ CH₃

H H CH₂ 2.0096 CH₃ CH₃

H F CH₂ 2.0097 CH₃ CH₃

H Cl CH₂ 2.0098 CH₃ CH₃

H H CH₂ 2.0099 CH₃ CH₃

H F CH₂ 2.0100 CH₃ CH₃

H Cl CH₂ 2.0101 CH₃ CH₃

H H CH₂ 2.0102 H CH₃ CH₂OCH₂CH₂OCH₃ H F CH₂ 2.0103 H CH₃ CH₂OCH₂CH₂OCH₃ H Cl CH₂ 2.0104 H CH₃ CH₂OCH₂CH₂OCH₃ H H CH₂ 2.0105 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ H F CH₂ 2.0106 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ H Cl CH₂ 2.0107 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ H H CH₂ 2.0108 H CH₃ CH₂N(CH₃)SO₂CH₃ H F CH₂ 2.0109 H CH₃ CH₂N(CH₃)SO₂CH₃ H Cl CH₂ 2.0110 H CH₃ CH₂N(CH₃)SO₂CH₃ H H CH₂ 2.0111 H CH₃ CH₂OCH₂Ph H F CH₂ 2.0112 H CH₃ CH₂OCH₂Ph H Cl CH₂ 2.0113 H CH₃ CH₂OCH₂Ph H H CH₂ 2.0114 H CH₃ CH₂OCH₂CH₂OH H F CH₂ 2.0115 H CH₃ CH₂OCH₂CH₂OH H Cl CH₂ 2.0116 H CH₃ CH₂OCH₂CH₂OH H H CH₂ 2.0117 H CH₃ CH₂OCH₂CH₂Cl H F CH₂ 2.0118 H CH₃ CH₂OCH₂CH₂Cl H Cl CH₂ 2.0119 H CH₃ CH₂OCH₂CH₂Cl H H CH₂ 2.0120 H CH₃ CH₂OCH₂CF₃ H F CH₂ 2.0121 H CH₃ CH₂OCH₂CF₃ H Cl CH₂ 2.0122 H CH₃ CH₂OCH₂CF₃ H H CH₂ 2.0123 H CH₃ CH₂OCH₂CH═CH₂ H F CH₂ 2.0124 H CH₃ CH₂OCH₂CH═CH₂ H Cl CH₂ 2.0125 H CH₃ CH₂OCH₂CH═CH₂ H H CH₂ 2.0126 H CH₃ CH₂O(CO)CH₃ H F CH₂ 2.0127 H CH₃ CH₂O(CO)CH₃ H Cl CH₂ 2.0128 H CH₃ CH₂O(CO)CH₃ H H CH₂ 2.0129 H CH₃ CH₂OCH₂C≡CH H F CH₂ 2.0130 H CH₃ CH₂OCH₂C≡CH H Cl CH₂ 2.0131 H CH₃ CH₂OCH₂C≡CH H H CH₂ 2.0132 H CH₃ CH₂OCH₂C≡CCH₃ H F CH₂ 2.0133 H CH₃ CH₂OCH₂C≡CCH₃ H Cl CH₂ 2.0134 H CH₃ CH₂OCH₂C≡CCH₃ H H CH₂ 2.0135 H CH₃

H F CH₂ 2.0136 H CH₃

H Cl CH₂ 2.0137 H CH₃

H H CH₂ 2.0138 H CH₃

H F CH₂ 2.0139 H CH₃

H Cl CH₂ 2.0140 H CH₃

H H CH₂ 2.0141 H CH₃

H F CH₂ 2.0142 H CH₃

H Cl CH₂ 2.0143 H CH₃

H H CH₂ 2.0144 H CH₃

H F CH₂ 2.0145 H CH₃

H Cl CH₂ 2.0146 H CH₃

H H CH₂ 2.0147 H CH₃

H F CH₂ 2.0148 H CH₃

H Cl CH₂ 2.0149 H CH₃

H H CH₂ 2.0150 H CH₃

H F CH₂ 2.0151 H CH₃

H Cl CH₂ 2.0152 H CH₃

H H CH₂ 2.0153 H H CH₂OCH₂CH₂OCH₃ CH₃ F CH₂ 2.0154 H H CH₂OCH₂CH₂OCH₃ CH₃ Cl CH₂ 2.0155 H H CH₂OCH₂CH₂OCH₃ CH₃ H CH₂ 2.0156 H H CH₂OCH₂CH₂OCH₂CH₃ CH₃ F CH₂ 2.0157 H H CH₂OCH₂CH₂OCH₂CH₃ CH₃ Cl CH₂ 2.0158 H H CH₂OCH₂CH₂OCH₂CH₃ CH₃ H CH₂ 2.0159 H H CH₂N(CH₃)SO₂CH₃ CH₃ F CH₂ 2.0160 H H CH₂N(CH₃)SO₂CH₃ CH₃ Cl CH₂ 2.0161 H H CH₂N(CH₃)SO₂CH₃ CH₃ H CH₂ 2.0162 H H CH₂OCH₂Ph CH₃ F CH₂ 2.0163 H H CH₂OCH₂Ph CH₃ Cl CH₂ 2.0164 H H CH₂OCH₂Ph CH₃ H CH₂ 2.0165 H H CH₂OCH₂CH₂OH CH₃ F CH₂ 2.0166 H H CH₂OCH₂CH₂OH CH₃ Cl CH₂ 2.0167 H H CH₂OCH₂CH₂OH CH₃ H CH₂ 2.0168 H H CH₂OCH₂CH₂Cl CH₃ F CH₂ 2.0169 H H CH₂OCH₂CH₂Cl CH₃ Cl CH₂ 2.0170 H H CH₂OCH₂CH₂Cl CH₃ H CH₂ 2.0171 H H CH₂OCH₂CF₃ CH₃ F CH₂ 2.0172 H H CH₂OCH₂CF₃ CH₃ Cl CH₂ 2.0173 H H CH₂OCH₂CF₃ CH₃ H CH₂ 2.0174 H H CH₂OCH₂CH═CH₂ CH₃ F CH₂ 2.0175 H H CH₂OCH₂CH═CH₂ CH₃ Cl CH₂ 2.0176 H H CH₂OCH₂CH═CH₂ CH₃ H CH₂ 2.0177 H H CH₂O(CO)CH₃ CH₃ F CH₂ 2.0178 H H CH₂O(CO)CH₃ CH₃ Cl CH₂ 2.0179 H H CH₂O(CO)CH₃ CH₃ H CH₂ 2.0180 H H CH₂OCH₂C≡CH CH₃ F CH₂ 2.0181 H H CH₂OCH₂C≡CH CH₃ Cl CH₂ 2.0182 H H CH₂OCH₂C≡CH CH₃ H CH₂ 2.0183 H H CH₂OCH₂C≡CCH₃ CH₃ F CH₂ 2.0184 H H CH₂OCH₂C≡CCH₃ CH₃ Cl CH₂ 2.0185 H H CH₂OCH₂C≡CCH₃ CH₃ H CH₂ 2.0186 H H

CH₃ F CH₂ 2.0187 H H

CH₃ Cl CH₂ 2.0188 H H

CH₃ H CH₂ 2.0189 H H

CH₃ F CH₂ 2.0190 H H

CH₃ Cl CH₂ 2.0191 H H

CH₃ H CH₂ 2.0192 H H

CH₃ F CH₂ 2.0193 H H

CH₃ Cl CH₂ 2.0194 H H

CH₃ H CH₂ 2.0195 H H

CH₃ F CH₂ 2.0196 H H

CH₃ Cl CH₂ 2.0197 H H

CH₃ H CH₂ 2.0198 H H

CH₃ F CH₂ 2.0199 H H

CH₃ Cl CH₂ 2.0200 H H

CH₃ H CH₂ 2.0201 H H

CH₃ F CH₂ 2.0202 H H

CH₃ Cl CH₂ 2.0203 H H

CH₃ H CH₂ 2.0204 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ CH₃ F CH₂ 2.0205 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ CH₃ Cl CH₂ 2.0206 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ CH₃ H CH₂ 2.0207 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ CH₃ F CH₂ 2.0208 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ CH₃ Cl CH₂ 2.0209 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ CH₃ H CH₂ 2.0210 CH₃ CH₃ CH₂N(CH₃)SO₂CH₃ CH₃ F CH₂ 2.0211 CH₃ CH₃ CH₂N(CH₃)SO₂CH₃ CH₃ Cl CH₂ 2.0212 CH₃ CH₃ CH₂N(CH₃)SO₂CH₃ CH₃ H CH₂ 2.0213 CH₃ CH₃ CH₂OCH₂Ph CH₃ F CH₂ 2.0214 CH₃ CH₃ CH₂OCH₂Ph CH₃ Cl CH₂ 2.0215 CH₃ CH₃ CH₂OCH₂Ph CH₃ H CH₂ 2.0216 CH₃ CH₃ CH₂OCH₂CH₂OH CH₃ F CH₂ 2.0217 CH₃ CH₃ CH₂OCH₂CH₂OH CH₃ Cl CH₂ 2.0218 CH₃ CH₃ CH₂OCH₂CH₂OH CH₃ H CH₂ 2.0219 CH₃ CH₃ CH₂OCH₂CH₂Cl CH₃ F CH₂ 2.0220 CH₃ CH₃ CH₂OCH₂CH₂Cl CH₃ Cl CH₂ 2.0221 CH₃ CH₃ CH₂OCH₂CH₂Cl CH₃ H CH₂ 2.0222 CH₃ CH₃ CH₂OCH₂CF₃ CH₃ F CH₂ 2.0223 CH₃ CH₃ CH₂OCH₂CF₃ CH₃ Cl CH₂ 2.0224 CH₃ CH₃ CH₂OCH₂CF₃ CH₃ H CH₂ 2.0225 CH₃ CH₃ CH₂OCH₂CH═CH₂ CH₃ F CH₂ 2.0226 CH₃ CH₃ CH₂OCH₂CH═CH₂ CH₃ Cl CH₂ 2.0227 CH₃ CH₃ CH₂OCH₂CH═CH₂ CH₃ H CH₂ 2.0228 CH₃ CH₃ CH₂O(CO)CH₃ CH₃ F CH₂ 2.0229 CH₃ CH₃ CH₂O(CO)CH₃ CH₃ Cl CH₂ 2.0230 CH₃ CH₃ CH₂O(CO)CH₃ CH₃ H CH₂ 2.0231 CH₃ CH₃ CH₂OCH₂C≡CH CH₃ F CH₂ 2.0232 CH₃ CH₃ CH₂OCH₂C≡CH CH₃ Cl CH₂ 2.0233 CH₃ CH₃ CH₂OCH₂C≡CH CH₃ H CH₂ 2.0234 CH₃ CH₃ CH₂OCH₂C≡CCH₃ CH₃ F CH₂ 2.0235 CH₃ CH₃ CH₂OCH₂C≡CCH₃ CH₃ Cl CH₂ 2.0236 CH₃ CH₃ CH₂OCH₂C≡CCH₃ CH₃ H CH₂ 2.0237 CH₃ CH₃

CH₃ F CH₂ 2.0238 CH₃ CH₃

CH₃ Cl CH₂ 2.0239 CH₃ CH₃

CH₃ H CH₂ 2.0240 CH₃ CH₃

CH₃ F CH₂ 2.0241 CH₃ CH₃

CH₃ Cl CH₂ 2.0242 CH₃ CH₃

CH₃ H CH₂ 2.0243 CH₃ CH₃

CH₃ F CH₂ 2.0244 CH₃ CH₃

CH₃ Cl CH₂ 2.0245 CH₃ CH₃

CH₃ H CH₂ 2.0246 CH₃ CH₃

CH₃ F CH₂ 2.0247 CH₃ CH₃

CH₃ Cl CH₂ 2.0248 CH₃ CH₃

CH₃ H CH₂ 2.0249 CH₃ CH₃

CH₃ F CH₂ 2.0250 CH₃ CH₃

CH₃ Cl CH₂ 2.0251 CH₃ CH₃

CH₃ H CH₂ 2.0252 CH₃ CH₃

CH₃ F CH₂ 2.0253 CH₃ CH₃

CH₃ Cl CH₂ 2.0254 CH₃ CH₃

CH₃ H CH₂ 2.0255 H CH₃ CH₂OCH₂CH₂OCH₃ CH₃ F CH₂ 2.0256 H CH₃ CH₂OCH₂CH₂OCH₃ CH₃ Cl CH₂ 2.0257 H CH₃ CH₂OCH₂CH₂OCH₃ CH₃ H CH₂ 2.0258 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ CH₃ F CH₂ 2.0259 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ CH₃ Cl CH₂ 2.0260 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ CH₃ H CH₂ 2.0261 H CH₃ CH₂N(CH₃)SO₂CH₃ CH₃ F CH₂ 2.0262 H CH₃ CH₂N(CH₃)SO₂CH₃ CH₃ Cl CH₂ 2.0263 H CH₃ CH₂N(CH₃)SO₂CH₃ CH₃ H CH₂ 2.0264 H CH₃ CH₂OCH₂Ph CH₃ F CH₂ 2.0265 H CH₃ CH₂OCH₂Ph CH₃ Cl CH₂ 2.0266 H CH₃ CH₂OCH₂Ph CH₃ H CH₂ 2.0267 H CH₃ CH₂OCH₂CH₂OH CH₃ F CH₂ 2.0268 H CH₃ CH₂OCH₂CH₂OH CH₃ Cl CH₂ 2.0269 H CH₃ CH₂OCH₂CH₂OH CH₃ H CH₂ 2.0270 H CH₃ CH₂OCH₂CH₂Cl CH₃ F CH₂ 2.0271 H CH₃ CH₂OCH₂CH₂Cl CH₃ Cl CH₂ 2.0272 H CH₃ CH₂OCH₂CH₂Cl CH₃ H CH₂ 2.0273 H CH₃ CH₂OCH₂CF₃ CH₃ F CH₂ 2.0274 H CH₃ CH₂OCH₂CF₃ CH₃ Cl CH₂ 2.0275 H CH₃ CH₂OCH₂CF₃ CH₃ H CH₂ 2.0276 H CH₃ CH₂OCH₂CH═CH₂ CH₃ F CH₂ 2.0277 H CH₃ CH₂OCH₂CH═CH₂ CH₃ Cl CH₂ 2.0278 H CH₃ CH₂OCH₂CH═CH₂ CH₃ H CH₂ 2.0279 H CH₃ CH₂O(CO)CH₃ CH₃ F CH₂ 2.0280 H CH₃ CH₂O(CO)CH₃ CH₃ Cl CH₂ 2.0281 H CH₃ CH₂O(CO)CH₃ CH₃ H CH₂ 2.0282 H CH₃ CH₂OCH₂C≡CH CH₃ F CH₂ 2.0283 H CH₃ CH₂OCH₂C≡CH CH₃ Cl CH₂ 2.0284 H CH₃ CH₂OCH₂C≡CH CH₃ H CH₂ 2.0285 H CH₃ CH₂OCH₂C≡CCH₃ CH₃ F CH₂ 2.0286 H CH₃ CH₂OCH₂C≡CCH₃ CH₃ Cl CH₂ 2.0287 H CH₃ CH₂OCH₂C≡CCH₃ CH₃ H CH₂ 2.0288 H CH₃

CH₃ F CH₂ 2.0289 H CH₃

CH₃ Cl CH₂ 2.0290 H CH₃

CH₃ H CH₂ 2.0291 H CH₃

CH₃ F CH₂ 2.0292 H CH₃

CH₃ Cl CH₂ 2.0293 H CH₃

CH₃ H CH₂ 2.0294 H CH₃

CH₃ F CH₂ 2.0295 H CH₃

CH₃ Cl CH₂ 2.0296 H CH₃

CH₃ H CH₂ 2.0297 H CH₃

CH₃ F CH₂ 2.0298 H CH₃

CH₃ Cl CH₂ 2.0299 H CH₃

CH₃ H CH₂ 2.0300 H CH₃

CH₃ F CH₂ 2.0301 H CH₃

CH₃ Cl CH₂ 2.0302 H CH₃

CH₃ H CH₂ 2.0303 H CH₃

CH₃ F CH₂ 2.0304 H CH₃

CH₃ Cl CH₂ 2.0305 H CH₃

CH₃ H CH₂

TABLE 3 Compounds of formula Id: (Id)

No. R₁ R₂ Z₁ R₃₀ X Y p Phys. data, remarks 3.0000 H H CH₂OCH₂CH₂OCH₃ H F CH₂ 0 3.0001 H H CH₂OCH₂CH₂OCH₃ H Cl CH₂ 0 3.0002 H H CH₂OCH₂CH₂OCH₃ H H CH₂ 0 3.0003 H H CH₂OCH₂CH₂OCH₂CH₃ H F CH₂ 0 3.0004 H H CH₂OCH₂CH₂OCH₂CH₃ H Cl CH₂ 0 3.0005 H H CH₂OCH₂CH₂OCH₂CH₃ H H CH₂ 0 3.0006 H H CH₂N(CH₃)SO₂CH₃ H F CH₂ 0 3.0007 H H CH₂N(CH₃)SO₂CH₃ H Cl CH₂ 0 3.0008 H H CH₂N(CH₃)SO₂CH₃ H H CH₂ 0 3.0009 H H CH₂OCH₂Ph H F CH₂ 0 3.0010 H H CH₂OCH₂Ph H Cl CH₂ 0 3.0011 H H CH₂OCH₂Ph H H CH₂ 0 3.0012 H H CH₂OCH₂CH₂OH H F CH₂ 0 3.0013 H H CH₂OCH₂CH₂OH H Cl CH₂ 0 3.0014 H H CH₂OCH₂CH₂OH H H CH₂ 0 3.0015 H H CH₂OCH₂CH₂Cl H F CH₂ 0 3.0016 H H CH₂OCH₂CH₂Cl H Cl CH₂ 0 3.0017 H H CH₂OCH₂CH₂Cl H H CH₂ 0 3.0018 H H CH₂OCH₂CF₃ H F CH₂ 0 3.0019 H H CH₂OCH₂CF₃ H Cl CH₂ 0 3.0020 H H CH₂OCH₂CF₃ H H CH₂ 0 3.0021 H H CH₂OCH₂CH═CH₂ H F CH₂ 0 3.0022 H H CH₂OCH₂CH═CH₂ H Cl CH₂ 0 3.0023 H H CH₂OCH₂CH═CH₂ H H CH₂ 0 3.0024 H H CH₂O(CO)CH₃ H F CH₂ 0 3.0025 H H CH₂O(CO)CH₃ H Cl CH₂ 0 3.0026 H H CH₂O(CO)CH₃ H H CH₂ 0 3.0027 H H CH₂OCH₂C≡CH H F CH₂ 0 3.0028 H H CH₂OCH₂C≡CH H Cl CH₂ 0 3.0029 H H CH₂OCH₂C≡CH H H CH₂ 0 3.0030 H H CH₂OCH₂C≡CCH₃ H F CH₂ 0 3.0031 H H CH₂OCH₂C≡CCH₃ H Cl CH₂ 0 3.0032 H H CH₂OCH₂C≡CCH₃ H H CH₂ 0 3.0033 H H

H F CH₂ 0 3.0034 H H

H Cl CH₂ 0 3.0035 H H

H H CH₂ 0 3.0036 H H

H F CH₂ 0 3.0037 H H

H Cl CH₂ 0 3.0038 H H

H H CH₂ 0 3.0039 H H

H F CH₂ 0 3.0040 H H

H Cl CH₂ 0 3.0041 H H

H H CH₂ 0 3.0042 H H

H F CH₂ 0 3.0043 H H

H Cl CH₂ 0 3.0044 H H

H H CH₂ 0 3.0045 H H

H F CH₂ 0 3.0046 H H

H Cl CH₂ 0 3.0047 H H

H H CH₂ 0 3.0048 H H

H F CH₂ 0 3.0049 H H

H Cl CH₂ 0 3.0050 H H

H H CH₂ 0 3.0051 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H F CH₂ 0 3.0052 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H Cl CH₂ 0 3.0053 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ H H CH₂ 0 3.0054 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ H F CH₂ 0 3.0055 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ H Cl CH₂ 0 3.0056 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ H H CH₂ 0 3.0057 CH₃ CH₃ CH₂N(CH₃)SO₂CH₃ H F CH₂ 0 3.0058 CH₃ CH₃ CH₂N(CH₃)SO₂CH₃ H Cl CH₂ 0 3.0059 CH₃ CH₃ CH₂N(CH₃)SO₂CH₃ H H CH₂ 0 3.0060 CH₃ CH₃ CH₂OCH₂Ph H F CH₂ 0 3.0061 CH₃ CH₃ CH₂OCH₂Ph H Cl CH₂ 0 3.0062 CH₃ CH₃ CH₂OCH₂Ph H H CH₂ 0 3.0063 CH₃ CH₃ CH₂OCH₂CH₂OH H F CH₂ 0 3.0064 CH₃ CH₃ CH₂OCH₂CH₂OH H Cl CH₂ 0 3.0065 CH₃ CH₃ CH₂OCH₂CH₂OH H H CH₂ 0 3.0066 CH₃ CH₃ CH₂OCH₂CH₂Cl H F CH₂ 0 3.0067 CH₃ CH₃ CH₂OCH₂CH₂Cl H Cl CH₂ 0 3.0068 CH₃ CH₃ CH₂OCH₂CH₂Cl H H CH₂ 0 3.0069 CH₃ CH₃ CH₂OCH₂CF₃ H F CH₂ 0 3.0070 CH₃ CH₃ CH₂OCH₂CF₃ H Cl CH₂ 0 3.0071 CH₃ CH₃ CH₂OCH₂CF₃ H H CH₂ 0 3.0072 CH₃ CH₃ CH₂OCH₂CH═CH₂ H F CH₂ 0 3.0073 CH₃ CH₃ CH₂OCH₂CH═CH₂ H Cl CH₂ 0 3.0074 CH₃ CH₃ CH₂OCH₂CH═CH₂ H H CH₂ 0 3.0075 CH₃ CH₃ CH₂O(CO)CH₃ H F CH₂ 0 3.0076 CH₃ CH₃ CH₂O(CO)CH₃ H Cl CH₂ 0 3.0077 CH₃ CH₃ CH₂O(CO)CH₃ H H CH₂ 0 3.0078 CH₃ CH₃ CH₂OCH₂C≡CH H F CH₂ 0 3.0079 CH₃ CH₃ CH₂OCH₂C≡CH H Cl CH₂ 0 3.0080 CH₃ CH₃ CH₂OCH₂C≡CH H H CH₂ 0 3.0081 CH₃ CH₃ CH₂OCH₂C≡CCH₃ H F CH₂ 0 3.0082 CH₃ CH₃ CH₂OCH₂C≡CCH₃ H Cl CH₂ 0 3.0083 CH₃ CH₃ CH₂OCH₂C≡CCH₃ H H CH₂ 0 3.0084 CH₃ CH₃

H F CH₂ 0 3.0085 CH₃ CH₃

H Cl CH₂ 0 3.0086 CH₃ CH₃

H H CH₂ 0 3.0087 CH₃ CH₃

H F CH₂ 0 3.0088 CH₃ CH₃

H Cl CH₂ 0 3.0089 CH₃ CH₃

H H CH₂ 0 3.0090 CH₃ CH₃

H F CH₂ 0 3.0091 CH₃ CH₃

H Cl CH₂ 0 3.0092 CH₃ CH₃

H H CH₂ 0 3.0093 CH₃ CH₃

H F CH₂ 0 3.0094 CH₃ CH₃

H Cl CH₂ 0 3.0095 CH₃ CH₃

H H CH₂ 0 3.0096 CH₃ CH₃

H F CH₂ 0 3.0097 CH₃ CH₃

H Cl CH₂ 0 3.0098 CH₃ CH₃

H H CH₂ 0 3.0099 CH₃ CH₃

H F CH₂ 0 3.0100 CH₃ CH₃

H Cl CH₂ 0 3.0101 CH₃ CH₃

H H CH₂ 0 3.0102 H CH₃ CH₂OCH₂CH₂OCH₃ H F CH₂ 0 3.0103 H CH₃ CH₂OCH₂CH₂OCH₃ H Cl CH₂ 0 3.0104 H CH₃ CH₂OCH₂CH₂OCH₃ H H CH₂ 0 3.0105 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ H F CH₂ 0 3.0106 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ H Cl CH₂ 0 3.0107 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ H H CH₂ 0 3.0108 H CH₃ CH₂N(CH₃)SO₂CH₃ H F CH₂ 0 3.0109 H CH₃ CH₂N(CH₃)SO₂CH₃ H Cl CH₂ 0 3.0110 H CH₃ CH₂N(CH₃)SO₂CH₃ H H CH₂ 0 3.0111 H CH₃ CH₂OCH₂Ph H F CH₂ 0 3.0112 H CH₃ CH₂OCH₂Ph H Cl CH₂ 0 3.0113 H CH₃ CH₂OCH₂Ph H H CH₂ 0 3.0114 H CH₃ CH₂OCH₂CH₂OH H F CH₂ 0 3.0115 H CH₃ CH₂OCH₂CH₂OH H Cl CH₂ 0 3.0116 H CH₃ CH₂OCH₂CH₂OH H H CH₂ 0 3.0117 H CH₃ CH₂OCH₂CH₂Cl H F CH₂ 0 3.0118 H CH₃ CH₂OCH₂CH₂Cl H Cl CH₂ 0 3.0119 H CH₃ CH₂OCH₂CH₂Cl H H CH₂ 0 3.0120 H CH₃ CH₂OCH₂CF₃ H F CH₂ 0 3.0121 H CH₃ CH₂OCH₂CF₃ H Cl CH₂ 0 3.0122 H CH₃ CH₂OCH₂CF₃ H H CH₂ 0 3.0123 H CH₃ CH₂OCH₂CH═CH₂ H F CH₂ 0 3.0124 H CH₃ CH₂OCH₂CH═CH₂ H Cl CH₂ 0 3.0125 H CH₃ CH₂OCH₂CH═CH₂ H H CH₂ 0 3.0126 H CH₃ CH₂O(CO)CH₃ H F CH₂ 0 3.0127 H CH₃ CH₂O(CO)CH₃ H Cl CH₂ 0 3.0128 H CH₃ CH₂O(CO)CH₃ H H CH₂ 0 3.0129 H CH₃ CH₂OCH₂C≡CH H F CH₂ 0 3.0130 H CH₃ CH₂OCH₂C≡CH H Cl CH₂ 0 3.0131 H CH₃ CH₂OCH₂C≡CH H H CH₂ 0 3.0132 H CH₃ CH₂OCH₂C≡CCH₃ H F CH₂ 0 3.0133 H CH₃ CH₂OCH₂C≡CCH₃ H Cl CH₂ 0 3.0134 H CH₃ CH₂OCH₂C≡CCH₃ H H CH₂ 0 3.0135 H CH₃

H F CH₂ 0 3.0136 H CH₃

H Cl CH₂ 0 3.0137 H CH₃

H H CH₂ 0 3.0138 H CH₃

H F CH₂ 0 3.0139 H CH₃

H Cl CH₂ 0 3.0140 H CH₃

H H CH₂ 0 3.0141 H CH₃

H F CH₂ 0 3.0142 H CH₃

H Cl CH₂ 0 3.0143 H CH₃

H H CH₂ 0 3.0144 H CH₃

H F CH₂ 0 3.0145 H CH₃

H Cl CH₂ 0 3.0146 H CH₃

H H CH₂ 0 3.0147 H CH₃

H F CH₂ 0 3.0148 H CH₃

H Cl CH₂ 0 3.0149 H CH₃

H H CH₂ 0 3.0150 H CH₃

H F CH₂ 0 3.0151 H CH₃

H Cl CH₂ 0 3.0152 H CH₃

H H CH₂ 0 3.0153 H H CH₂OCH₂CH₂OCH₃ CH₃ F CH₂ 0 3.0154 H H CH₂OCH₂CH₂OCH₃ CH₃ Cl CH₂ 0 3.0155 H H CH₂OCH₂CH₂OCH₃ CH₃ H CH₂ 0 3.0156 H H CH₂OCH₂CH₂OCH₂CH₃ CH₃ F CH₂ 0 3.0157 H H CH₂OCH₂CH₂OCH₂CH₃ CH₃ Cl CH₂ 0 3.0158 H H CH₂OCH₂CH₂OCH₂CH₃ CH₃ H CH₂ 0 3.0159 H H CH₂N(CH₃)SO₂CH₃ CH₃ F CH₂ 0 3.0160 H H CH₂N(CH₃)SO₂CH₃ CH₃ Cl CH₂ 0 3.0161 H H CH₂N(CH₃)SO₂CH₃ CH₃ H CH₂ 0 3.0162 H H CH₂OCH₂Ph CH₃ F CH₂ 0 3.0163 H H CH₂OCH₂Ph CH₃ Cl CH₂ 0 3.0164 H H CH₂OCH₂Ph CH₃ H CH₂ 0 3.0165 H H CH₂OCH₂CH₂OH CH₃ F CH₂ 0 3.0166 H H CH₂OCH₂CH₂OH CH₃ Cl CH₂ 0 3.0167 H H CH₂OCH₂CH₂OH CH₃ H CH₂ 0 3.0168 H H CH₂OCH₂CH₂Cl CH₃ F CH₂ 0 3.0169 H H CH₂OCH₂CH₂Cl CH₃ Cl CH₂ 0 3.0170 H H CH₂OCH₂CH₂Cl CH₃ H CH₂ 0 3.0171 H H CH₂OCH₂CF₃ CH₃ F CH₂ 0 3.0172 H H CH₂OCH₂CF₃ CH₃ Cl CH₂ 0 3.0173 H H CH₂OCH₂CF₃ CH₃ H CH₂ 0 3.0174 H H CH₂OCH₂CH═CH₂ CH₃ F CH₂ 0 3.0175 H H CH₂OCH₂CH═CH₂ CH₃ Cl CH₂ 0 3.0176 H H CH₂OCH₂CH═CH₂ CH₃ H CH₂ 0 3.0177 H H CH₂O(CO)CH₃ CH₃ F CH₂ 0 3.0178 H H CH₂O(CO)CH₃ CH₃ Cl CH₂ 0 3.0179 H H CH₂O(CO)CH₃ CH₃ H CH₂ 0 3.0180 H H CH₂OCH₂C≡CH CH₃ F CH₂ 0 3.0181 H H CH₂OCH₂C≡CH CH₃ Cl CH₂ 0 3.0182 H H CH₂OCH₂C≡CH CH₃ H CH₂ 0 3.0183 H H CH₂OCH₂C≡CCH₃ CH₃ F CH₂ 0 3.0184 H H CH₂OCH₂C≡CCH₃ CH₃ Cl CH₂ 0 3.0185 H H CH₂OCH₂C≡CCH₃ CH₃ H CH₂ 0 3.0186 H H

CH₃ F CH₂ 0 3.0187 H H

CH₃ Cl CH₂ 0 3.0188 H H

CH₃ H CH₂ 0 3.0189 H H

CH₃ F CH₂ 0 3.0190 H H

CH₃ Cl CH₂ 0 3.0191 H H

CH₃ H CH₂ 0 3.0192 H H

CH₃ F CH₂ 0 3.0193 H H

CH₃ Cl CH₂ 0 3.0194 H H

CH₃ H CH₂ 0 3.0195 H H

CH₃ F CH₂ 0 3.0196 H H

CH₃ Cl CH₂ 0 3.0197 H H

CH₃ H CH₂ 0 3.0198 H H

CH₃ F CH₂ 0 3.0199 H H

CH₃ Cl CH₂ 0 3.0200 H H

CH₃ H CH₂ 0 3.0201 H H

CH₃ F CH₂ 0 3.0202 H H

CH₃ Cl CH₂ 0 3.0203 H H

CH₃ H CH₂ 0 3.0204 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ CH₃ F CH₂ 0 3.0205 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ CH₃ Cl CH₂ 0 3.0206 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ CH₃ H CH₂ 0 3.0207 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ CH₃ F CH₂ 0 3.0208 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ CH₃ Cl CH₂ 0 3.0209 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ CH₃ H CH₂ 0 3.0210 CH₃ CH₃ CH₂N(CH₃)SO₂CH₃ CH₃ F CH₂ 0 3.0211 CH₃ CH₃ CH₂N(CH₃)SO₂CH₃ CH₃ Cl CH₂ 0 3.0212 CH₃ CH₃ CH₂N(CH₃)SO₂CH₃ CH₃ H CH₂ 0 3.0213 CH₃ CH₃ CH₂OCH₂Ph CH₃ F CH₂ 0 3.0214 CH₃ CH₃ CH₂OCH₂Ph CH₃ Cl CH₂ 0 3.0215 CH₃ CH₃ CH₂OCH₂Ph CH₃ H CH₂ 0 3.0216 CH₃ CH₃ CH₂OCH₂CH₂OH CH₃ F CH₂ 0 3.0217 CH₃ CH₃ CH₂OCH₂CH₂OH CH₃ Cl CH₂ 0 3.0218 CH₃ CH₃ CH₂OCH₂CH₂OH CH₃ H CH₂ 0 3.0219 CH₃ CH₃ CH₂OCH₂CH₂Cl CH₃ F CH₂ 0 3.0220 CH₃ CH₃ CH₂OCH₂CH₂Cl CH₃ Cl CH₂ 0 3.0221 CH₃ CH₃ CH₂OCH₂CH₂Cl CH₃ H CH₂ 0 3.0222 CH₃ CH₃ CH₂OCH₂CF₃ CH₃ F CH₂ 0 3.0223 CH₃ CH₃ CH₂OCH₂CF₃ CH₃ Cl CH₂ 0 3.0224 CH₃ CH₃ CH₂OCH₂CF₃ CH₃ H CH₂ 0 3.0225 CH₃ CH₃ CH₂OCH₂CH═CH₂ CH₃ F CH₂ 0 3.0226 CH₃ CH₃ CH₂OCH₂CH═CH₂ CH₃ Cl CH₂ 0 3.0227 CH₃ CH₃ CH₂OCH₂CH═CH₂ CH₃ H CH₂ 0 3.0228 CH₃ CH₃ CH₂O(CO)CH₃ CH₃ F CH₂ 0 3.0229 CH₃ CH₃ CH₂O(CO)CH₃ CH₃ Cl CH₂ 0 3.0230 CH₃ CH₃ CH₂O(CO)CH₃ CH₃ H CH₂ 0 3.0231 CH₃ CH₃ CH₂OCH₂C≡CH CH₃ F CH₂ 0 3.0232 CH₃ CH₃ CH₂OCH₂C≡CH CH₃ Cl CH₂ 0 3.0233 CH₃ CH₃ CH₂OCH₂C≡CH CH₃ H CH₂ 0 3.0234 CH₃ CH₃ CH₂OCH₂C≡CCH₃ CH₃ F CH₂ 0 3.0235 CH₃ CH₃ CH₂OCH₂C≡CCH₃ CH₃ Cl CH₂ 0 3.0236 CH₃ CH₃ CH₂OCH₂C≡CCH₃ CH₃ H CH₂ 0 3.0237 CH₃ CH₃

CH₃ F CH₂ 0 3.0238 CH₃ CH₃

CH₃ Cl CH₂ 0 3.0239 CH₃ CH₃

CH₃ H CH₂ 0 3.0240 CH₃ CH₃

CH₃ F CH₂ 0 3.0241 CH₃ CH₃

CH₃ Cl CH₂ 0 3.0242 CH₃ CH₃

CH₃ H CH₂ 0 3.0243 CH₃ CH₃

CH₃ F CH₂ 0 3.0244 CH₃ CH₃

CH₃ Cl CH₂ 0 3.0245 CH₃ CH₃

CH₃ H CH₂ 0 3.0246 CH₃ CH₃

CH₃ F CH₂ 0 3.0247 CH₃ CH₃

CH₃ Cl CH₂ 0 3.0248 CH₃ CH₃

CH₃ H CH₂ 0 3.0249 CH₃ CH₃

CH₃ F CH₂ 0 3.0250 CH₃ CH₃

CH₃ Cl CH₂ 0 3.0251 CH₃ CH₃

CH₃ H CH₂ 0 3.0252 CH₃ CH₃

CH₃ F CH₂ 0 3.0253 CH₃ CH₃

CH₃ Cl CH₂ 0 3.0254 CH₃ CH₃

CH₃ H CH₂ 0 3.0255 H CH₃ CH₂OCH₂CH₂OCH₃ CH₃ F CH₂ 0 3.0256 H CH₃ CH₂OCH₂CH₂OCH₃ CH₃ Cl CH₂ 0 3.0257 H CH₃ CH₂OCH₂CH₂OCH₃ CH₃ H CH₂ 0 3.0258 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ CH₃ F CH₂ 0 3.0259 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ CH₃ Cl CH₂ 0 3.0260 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ CH₃ H CH₂ 0 3.0261 H CH₃ CH₂N(CH₃)SO₂CH₃ CH₃ F CH₂ 0 3.0262 H CH₃ CH₂N(CH₃)SO₂CH₃ CH₃ Cl CH₂ 0 3.0263 H CH₃ CH₂N(CH₃)SO₂CH₃ CH₃ H CH₂ 0 3.0264 H CH₃ CH₂OCH₂Ph CH₃ F CH₂ 0 3.0265 H CH₃ CH₂OCH₂Ph CH₃ Cl CH₂ 0 3.0266 H CH₃ CH₂OCH₂Ph CH₃ H CH₂ 0 3.0267 H CH₃ CH₂OCH₂CH₂OH CH₃ F CH₂ 0 3.0268 H CH₃ CH₂OCH₂CH₂OH CH₃ Cl CH₂ 0 3.0269 H CH₃ CH₂OCH₂CH₂OH CH₃ H CH₂ 0 3.0270 H CH₃ CH₂OCH₂CH₂Cl CH₃ F CH₂ 0 3.0271 H CH₃ CH₂OCH₂CH₂Cl CH₃ Cl CH₂ 0 3.0272 H CH₃ CH₂OCH₂CH₂Cl CH₃ H CH₂ 0 3.0273 H CH₃ CH₂OCH₂CF₃ CH₃ F CH₂ 0 3.0274 H CH₃ CH₂OCH₂CF₃ CH₃ Cl CH₂ 0 3.0275 H CH₃ CH₂OCH₂CF₃ CH₃ H CH₂ 0 3.0276 H CH₃ CH₂OCH₂CH═CH₂ CH₃ F CH₂ 0 3.0277 H CH₃ CH₂OCH₂CH═CH₂ CH₃ Cl CH₂ 0 3.0278 H CH₃ CH₂OCH₂CH═CH₂ CH₃ H CH₂ 0 3.0279 H CH₃ CH₂O(CO)CH₃ CH₃ F CH₂ 0 3.0280 H CH₃ CH₂O(CO)CH₃ CH₃ Cl CH₂ 0 3.0281 H CH₃ CH₂O(CO)CH₃ CH₃ H CH₂ 0 3.0282 H CH₃ CH₂OCH₂C≡CH CH₃ F CH₂ 0 3.0283 H CH₃ CH₂OCH₂C≡CH CH₃ Cl CH₂ 0 3.0284 H CH₃ CH₂OCH₂C≡CH CH₃ H CH₂ 0 3.0285 H CH₃ CH₂OCH₂C≡CCH₃ CH₃ F CH₂ 0 3.0286 H CH₃ CH₂OCH₂C≡CCH₃ CH₃ Cl CH₂ 0 3.0287 H CH₃ CH₂OCH₂C≡CCH₃ CH₃ H CH₂ 0 3.0288 H CH₃

CH₃ F CH₂ 0 3.0289 H CH₃

CH₃ Cl CH₂ 0 3.0290 H CH₃

CH₃ H CH₂ 0 3.0291 H CH₃

CH₃ F CH₂ 0 3.0292 H CH₃

CH₃ Cl CH₂ 0 3.0293 H CH₃

CH₃ H CH₂ 0 3.0294 H CH₃

CH₃ F CH₂ 0 3.0295 H CH₃

CH₃ Cl CH₂ 0 3.0296 H CH₃

CH₃ H CH₂ 0 3.0297 H CH₃

CH₃ F CH₂ 0 3.0298 H CH₃

CH₃ Cl CH₂ 0 3.0299 H CH₃

CH₃ H CH₂ 0 3.0300 H CH₃

CH₃ F CH₂ 0 3.0301 H CH₃

CH₃ Cl CH₂ 0 3.0302 H CH₃

CH₃ H CH₂ 0 3.0303 H CH₃

CH₃ F CH₂ 0 3.0304 H CH₃

CH₃ Cl CH₂ 0 3.0305 H CH₃

CH₃ H CH₂ 0 3.0306 H H CH₂OCH₂CH₂OCH₃ CH₃ F CH₂ 1 3.0307 H H CH₂OCH₂CH₂OCH₃ CH₃ Cl CH₂ 1 3.0308 H H CH₂OCH₂CH₂OCH₃ CH₃ H CH₂ 1 3.0309 H H CH₂OCH₂CH₂OCH₂CH₃ CH₃ F CH₂ 1 3.0310 H H CH₂OCH₂CH₂OCH₂CH₃ CH₃ Cl CH₂ 1 3.0311 H H CH₂OCH₂CH₂OCH₂CH₃ CH₃ H CH₂ 1 3.0312 H H CH₂N(CH₃)SO₂CH₃ CH₃ F CH₂ 1 3.0313 H H CH₂N(CH₃)SO₂CH₃ CH₃ Cl CH₂ 1 3.0314 H H CH₂N(CH₃)SO₂CH₃ CH₃ H CH₂ 1 3.0315 H H CH₂OCH₂Ph CH₃ F CH₂ 1 3.0316 H H CH₂OCH₂Ph CH₃ Cl CH₂ 1 3.0317 H H CH₂OCH₂Ph CH₃ H CH₂ 1 3.0318 H H CH₂OCH₂CH₂OH CH₃ F CH₂ 1 3.0319 H H CH₂OCH₂CH₂OH CH₃ Cl CH₂ 1 3.0320 H H CH₂OCH₂CH₂OH CH₃ H CH₂ 1 3.0321 H H CH₂OCH₂CH₂Cl CH₃ F CH₂ 1 3.0322 H H CH₂OCH₂CH₂Cl CH₃ Cl CH₂ 1 3.0323 H H CH₂OCH₂CH₂Cl CH₃ H CH₂ 1 3.0324 H H CH₂OCH₂CF₃ CH₃ F CH₂ 1 3.0325 H H CH₂OCH₂CF₃ CH₃ Cl CH₂ 1 3.0326 H H CH₂OCH₂CF₃ CH₃ H CH₂ 1 3.0327 H H CH₂OCH₂CH═CH₂ CH₃ F CH₂ 1 3.0328 H H CH₂OCH₂CH═CH₂ CH₃ Cl CH₂ 1 3.0329 H H CH₂OCH₂CH═CH₂ CH₃ H CH₂ 1 3.0330 H H CH₂O(CO)CH₃ CH₃ F CH₂ 1 3.0331 H H CH₂O(CO)CH₃ CH₃ Cl CH₂ 1 3.0332 H H CH₂O(CO)CH₃ CH₃ H CH₂ 1 3.0333 H H CH₂OCH₂C≡CH CH₃ F CH₂ 1 3.0334 H H CH₂OCH₂C≡CH CH₃ Cl CH₂ 1 3.0335 H H CH₂OCH₂C≡CH CH₃ H CH₂ 1 3.0336 H H CH₂OCH₂C≡CCH₃ CH₃ F CH₂ 1 3.0337 H H CH₂OCH₂C≡CCH₃ CH₃ Cl CH₂ 1 3.0338 H H CH₂OCH₂C≡CCH₃ CH₃ H CH₂ 1 3.0339 H H

CH₃ F CH₂ 1 3.0340 H H

CH₃ Cl CH₂ 1 3.0341 H H

CH₃ H CH₂ 1 3.0342 H H

CH₃ F CH₂ 1 3.0343 H H

CH₃ Cl CH₂ 1 3.0344 H H

CH₃ H CH₂ 1 3.0345 H H

CH₃ F CH₂ 1 3.0346 H H

CH₃ Cl CH₂ 1 3.0347 H H

CH₃ H CH₂ 1 3.0348 H H

CH₃ F CH₂ 1 3.0349 H H

CH₃ Cl CH₂ 1 3.0350 H H

CH₃ H CH₂ 1 3.0351 H H

CH₃ F CH₂ 1 3.0352 H H

CH₃ Cl CH₂ 1 3.0353 H H

CH₃ H CH₂ 1 3.0354 H H

CH₃ F CH₂ 1 3.0355 H H

CH₃ Cl CH₂ 1 3.0356 H H

CH₃ H CH₂ 1 3.0357 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ CH₃ F CH₂ 1 3.0358 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ CH₃ Cl CH₂ 1 3.0359 CH₃ CH₃ CH₂OCH₂CH₂OCH₃ CH₃ H CH₂ 1 3.0360 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ CH₃ F CH₂ 1 3.0361 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ CH₃ Cl CH₂ 1 3.0362 CH₃ CH₃ CH₂OCH₂CH₂OCH₂CH₃ CH₃ H CH₂ 1 3.0363 CH₃ CH₃ CH₂N(CH₃)SO₂CH₃ CH₃ F CH₂ 1 3.0364 CH₃ CH₃ CH₂N(CH₃)SO₂CH₃ CH₃ Cl CH₂ 1 3.0365 CH₃ CH₃ CH₂N(CH₃)SO₂CH₃ CH₃ H CH₂ 1 3.0366 CH₃ CH₃ CH₂OCH₂Ph CH₃ F CH₂ 1 3.0367 CH₃ CH₃ CH₂OCH₂Ph CH₃ Cl CH₂ 1 3.0368 CH₃ CH₃ CH₂OCH₂Ph CH₃ H CH₂ 1 3.0369 CH₃ CH₃ CH₂OCH₂CH₂OH CH₃ F CH₂ 1 3.0370 CH₃ CH₃ CH₂OCH₂CH₂OH CH₃ Cl CH₂ 1 3.0371 CH₃ CH₃ CH₂OCH₂CH₂OH CH₃ H CH₂ 1 3.0372 CH₃ CH₃ CH₂OCH₂CH₂Cl CH₃ F CH₂ 1 3.0373 CH₃ CH₃ CH₂OCH₂CH₂Cl CH₃ Cl CH₂ 1 3.0374 CH₃ CH₃ CH₂OCH₂CH₂Cl CH₃ H CH₂ 1 3.0375 CH₃ CH₃ CH₂OCH₂CF₃ CH₃ F CH₂ 1 3.0376 CH₃ CH₃ CH₂OCH₂CF₃ CH₃ Cl CH₂ 1 3.0377 CH₃ CH₃ CH₂OCH₂CF₃ CH₃ H CH₂ 1 3.0378 CH₃ CH₃ CH₂OCH₂CH═CH₂ CH₃ F CH₂ 1 3.0379 CH₃ CH₃ CH₂OCH₂CH═CH₂ CH₃ Cl CH₂ 1 3.0380 CH₃ CH₃ CH₂OCH₂CH═CH₂ CH₃ H CH₂ 1 3.0381 CH₃ CH₃ CH₂O(CO)CH₃ CH₃ F CH₂ 1 3.0382 CH₃ CH₃ CH₂O(CO)CH₃ CH₃ Cl CH₂ 1 3.0383 CH₃ CH₃ CH₂O(CO)CH₃ CH₃ H CH₂ 1 3.0384 CH₃ CH₃ CH₂OCH₂C≡CH CH₃ F CH₂ 1 3.0385 CH₃ CH₃ CH₂OCH₂C≡CH CH₃ Cl CH₂ 1 3.0386 CH₃ CH₃ CH₂OCH₂C≡CH CH₃ H CH₂ 1 3.0387 CH₃ CH₃ CH₂OCH₂C≡CCH₃ CH₃ F CH₂ 1 3.0388 CH₃ CH₃ CH₂OCH₂C≡CCH₃ CH₃ Cl CH₂ 1 3.0389 CH₃ CH₃ CH₂OCH₂C≡CCH₃ CH₃ H CH₂ 1 3.0390 CH₃ CH₃

CH₃ F CH₂ 1 3.0391 CH₃ CH₃

CH₃ Cl CH₂ 1 3.0392 CH₃ CH₃

CH₃ H CH₂ 1 3.0393 CH₃ CH₃

CH₃ F CH₂ 1 3.0394 CH₃ CH₃

CH₃ Cl CH₂ 1 3.0395 CH₃ CH₃

CH₃ H CH₂ 1 3.0396 CH₃ CH₃

CH₃ F CH₂ 1 3.0397 CH₃ CH₃

CH₃ Cl CH₂ 1 3.0398 CH₃ CH₃

CH₃ H CH₂ 1 3.0399 CH₃ CH₃

CH₃ F CH₂ 1 3.0400 CH₃ CH₃

CH₃ Cl CH₂ 1 3.0401 CH₃ CH₃

CH₃ H CH₂ 1 3.0402 CH₃ CH₃

CH₃ F CH₂ 1 3.0403 CH₃ CH₃

CH₃ Cl CH₂ 1 3.0404 CH₃ CH₃

CH₃ H CH₂ 1 3.0405 CH₃ CH₃

CH₃ F CH₂ 1 3.0406 CH₃ CH₃

CH₃ Cl CH₂ 1 3.0407 CH₃ CH₃

CH₃ H CH₂ 1 3.0408 H CH₃ CH₂OCH₂CH₂OCH₃ CH₃ F CH₂ 1 3.0409 H CH₃ CH₂OCH₂CH₂OCH₃ CH₃ Cl CH₂ 1 3.0410 H CH₃ CH₂OCH₂CH₂OCH₃ CH₃ H CH₂ 1 3.0411 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ CH₃ F CH₂ 1 3.0412 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ CH₃ Cl CH₂ 1 3.0413 H CH₃ CH₂OCH₂CH₂OCH₂CH₃ CH₃ H CH₂ 1 3.0414 H CH₃ CH₂N(CH₃)SO₂CH₃ CH₃ F CH₂ 1 3.0415 H CH₃ CH₂N(CH₃)SO₂CH₃ CH₃ Cl CH₂ 1 3.0416 H CH₃ CH₂N(CH₃)SO₂CH₃ CH₃ H CH₂ 1 3.0417 H CH₃ CH₂OCH₂Ph CH₃ F CH₂ 1 3.0418 H CH₃ CH₂OCH₂Ph CH₃ Cl CH₂ 1 3.0419 H CH₃ CH₂OCH₂Ph CH₃ H CH₂ 1 3.0420 H CH₃ CH₂OCH₂CH₂OH CH₃ F CH₂ 1 3.0421 H CH₃ CH₂OCH₂CH₂OH CH₃ Cl CH₂ 1 3.0422 H CH₃ CH₂OCH₂CH₂OH CH₃ H CH₂ 1 3.0423 H CH₃ CH₂OCH₂CH₂Cl CH₃ F CH₂ 1 3.0424 H CH₃ CH₂OCH₂CH₂Cl CH₃ Cl CH₂ 1 3.0425 H CH₃ CH₂OCH₂CH₂Cl CH₃ H CH₂ 1 3.0426 H CH₃ CH₂OCH₂CF₃ CH₃ F CH₂ 1 3.0427 H CH₃ CH₂OCH₂CF₃ CH₃ Cl CH₂ 1 3.0428 H CH₃ CH₂OCH₂CF₃ CH₃ H CH₂ 1 3.0429 H CH₃ CH₂OCH₂CH═CH₂ CH₃ F CH₂ 1 3.0430 H CH₃ CH₂OCH₂CH═CH₂ CH₃ Cl CH₂ 1 3.0431 H CH₃ CH₂OCH₂CH═CH₂ CH₃ H CH₂ 1 3.0432 H CH₃ CH₂O(CO)CH₃ CH₃ F CH₂ 1 3.0433 H CH₃ CH₂O(CO)CH₃ CH₃ Cl CH₂ 1 3.0434 H CH₃ CH₂O(CO)CH₃ CH₃ H CH₂ 1 3.0435 H CH₃ CH₂OCH₂C≡CH CH₃ F CH₂ 1 3.0436 H CH₃ CH₂OCH₂C≡CH CH₃ Cl CH₂ 1 3.0437 H CH₃ CH₂OCH₂C≡CH CH₃ H CH₂ 1 3.0438 H CH₃ CH₂OCH₂C≡CCH₃ CH₃ F CH₂ 1 3.0439 H CH₃ CH₂OCH₂C≡CCH₃ CH₃ Cl CH₂ 1 3.0440 H CH₃ CH₂OCH₂C≡CCH₃ CH₃ H CH₂ 1 3.0441 H CH₃

CH₃ F CH₂ 1 3.0442 H CH₃

CH₃ Cl CH₂ 1 3.0443 H CH₃

CH₃ H CH₂ 1 3.0444 H CH₃

CH₃ F CH₂ 1 3.0445 H CH₃

CH₃ Cl CH₂ 1 3.0446 H CH₃

CH₃ H CH₂ 1 3.0447 H CH₃

CH₃ F CH₂ 1 3.0448 H CH₃

CH₃ Cl CH₂ 1 3.0449 H CH₃

CH₃ H CH₂ 1 3.0450 H CH₃

CH₃ F CH₂ 1 3.0451 H CH₃

CH₃ Cl CH₂ 1 3.0452 H CH₃

CH₃ H CH₂ 1 3.0453 H CH₃

CH₃ F CH₂ 1 3.0454 H CH₃

CH₃ Cl CH₂ 1 3.0455 H CH₃

CH₃ H CH₂ 1 3.0456 H CH₃

CH₃ F CH₂ 1 3.0457 H CH₃

CH₃ Cl CH₂ 1 3.0458 H CH₃

CH₃ H CH₂ 1

TABLE 4 Intermediates of formulae Da and Db:

No. R₁ R₂ R₃ Y Xa Physical data 4.0001 H H OH CH₂ H see Example P9; tautomeric form Da 4.0002 H H OCH₃ CH₂ H 4.0003 H H OCH₂CH₃ CH₂ H 4.0004 H H OC(CH₃)₂ CH₂ H 4.0005 H H OH CH₂CH₂ H see Example P12; tautomeric form Da 4.0006 H H OCH₃ CH₂CH₂ H 4.0007 H H OCH₂CH₃ CH₂CH₂ H 4.0008 H H OC(CH₃)₂ CH₂CH₂ H 4.0009 H H OH O H ¹H NMR (300 MHz; CDCl₃) δ 6.35 (s, 2H); 5.66 (s, 1H); 3.78 (d, 1H); 3.43 (d, 1H); tautomeric form Da 4.0010 H H OCH₃ O H 4.0011 H H OCH₂CH₃ O H 4.0012 H H OC(CH₃)₂ O H 4.0013 H H OH NSO₂CH₃ H 4.0014 H H OCH₃ NSO₂CH₃ H 4.0015 H H OCH₂CH₃ NSO₂CH₃ H 4.0016 H H OC(CH₃)₂ NSO₂CH₃ H 4.0017 H H OH NC(O)C(CH₃)₃ H 4.0018 H H OCH₃ NC(O)C(CH₃)₃ H 4.0019 H H OCH₂CH₃ NC(O)C(CH₃)₃ H 4.0020 H H OC(CH₃)₂ NC(O)C(CH₃)₃ H 4.0021 H H OH CH₂ Cl 4.0022 H H OCH₃ CH₂ Cl 4.0023 H H OCH₂CH₃ CH₂ Cl 4.0024 H H OC(CH₃)₂ CH₂ Cl 4.0025 H H OH CH₂CH₂ Cl see Preparation Example P11 4.0026 H H OCH₃ CH₂CH₂ Cl 4.0027 H H OCH₂CH₃ CH₂CH₂ Cl 4.0028 H H OC(CH₃)₂ CH₂CH₂ Cl 4.0029 H H OH O Cl 4.0030 H H OCH₃ O Cl 4.0031 H H OCH₂CH₃ O Cl 4.0032 H H OC(CH₃)₂ O Cl 4.0033 H H OH NSO₂CH₃ Cl 4.0034 H H OCH₃ NSO₂CH₃ Cl 4.0035 H H OCH₂CH₃ NSO₂CH₃ Cl 4.0036 H H OC(CH₃)₂ NSO₂CH₃ Cl 4.0037 H H OH NC(O)C(CH₃)₃ Cl 4.0038 H H OCH₃ NC(O)C(CH₃)₃ Cl 4.0039 H H OCH₂CH₃ NC(O)C(CH₃)₃ Cl 4.0040 H H OC(CH₃)₂ NC(O)C(CH₃)₃ Cl 4.0041 H H OH CH₂ Br 4.0042 H H OCH₃ CH₂ Br 4.0043 H H OCH₂CH₃ CH₂ Br 4.0044 H H OC(CH₃)₂ CH₂ Br 4.0045 H H OH CH₂CH₂ Br 4.0046 H H OCH₃ CH₂CH₂ Br 4.0047 H H OCH₂CH₃ CH_(2CH) ₂ Br 4.0048 H H OC(CH₃)₂ CH_(2CH) ₂ Br 4.0049 H H OH O Br 4.0050 H H OCH₃ O Br 4.0051 H H OCH₂CH₃ O Br 4.0052 H H OC(CH₃)₂ O Br 4.0053 H H OH NSO₂CH₃ Br 4.0054 H H OCH₃ NSO₂CH₃ Br 4.0055 H H OCH₂CH₃ NSO₂CH₃ Br 4.0056 H H OC(CH₃)₂ NSO₂CH₃ Br 4.0057 H H OH NC(O)C(CH₃)₃ Br 4.0058 H H OCH₃ NC(O)C(CH₃)₃ Br 4.0059 H H OCH₂CH₃ NC(O)C(CH₃)₃ Br 4.0060 H H OC(CH₃)₂ NC(O)O(CH₃)₃ Br 4.0061 H CH₃ OH CH₂ H ¹H NMR (300 MHz; CDCl₃) δ 6.30 (m, 1H); 6.10 (m, 1H); 3.73 (d, 1H); 3.44 (d, 1H); 1.62 (s, 3H); tautomeric form Db 4.0062 H CH₃ OCH₃ CH₂ H 4.0063 H CH₃ OCH₂CH₃ CH₂ H 4.0064 H CH₃ OC(CH₃)₂ CH₂ H 4.0065 H CH₃ OH CH₂CH₂ H 4.0066 H CH₃ OCH₃ CH₂CH₂ H 4.0067 H CH₃ OCH₂CH₃ CH₂CH₂ H 4.0068 H CH₃ OC(CH₃)₂ CH₂CH₂ H 4.0069 H CH₃ OH O H 4.0070 H CH₃ OCH₃ O H 4.0071 H CH₃ OCH₂CH₃ O H 4.0072 H CH₃ OC(CH₃)₂ O H 4.0073 H CH₃ OH NSO₂CH₃ H 4.0074 H CH₃ OCH₃ NSO₂CH₃ H 4.0075 H CH₃ OCH₂CH₃ NSO₂CH₃ H 4.0076 H CH₃ OC(CH₃)₂ NSO₂CH₃ H 4.0077 H CH₃ OH NC(O)O(CH₃)₃ H 4.0078 H CH₃ OCH₃ NC(O)O(CH₃)₃ H 4.0079 H CH₃ OCH₂CH₃ NC(O)C(CH₃)₃ H 4.0080 H CH₃ OC(CH₃)₂ NC(O)O(CH₃)₃ H 4.0081 H CH₃ OH CH₂ Cl 4.0082 H CH₃ OCH₃ CH₂ Cl 4.0083 H CH₃ OCH₂CH₃ CH₂ Cl 4.0084 H CH₃ OC(CH₃)₂ CH₂ Cl 4.0085 H CH₃ OH CH₂CH₂ Cl 4.0086 H CH₃ OCH₃ CH₂CH₂ Cl 4.0087 H CH₃ OCH₂CH₃ CH₂CH₂ Cl 4.0088 H CH₃ OC(CH₃)₂ CH₂CH₂ Cl 4.0089 H CH₃ OH O Cl 4.0090 H CH₃ OCH₃ O Cl 4.0091 H CH₃ OCH₂CH₃ O Cl 4.0092 H CH₃ OC(CH₃)₂ O Cl 4.0093 H CH₃ OH NSO₂CH₃ Cl 4.0094 H CH₃ OCH₃ NSO₂CH₃ Cl 4.0095 H CH₃ OCH₂CH₃ NSO₂CH₃ Cl 4.0096 H CH₃ OC(CH₃)₂ NSO₂CH₃ Cl 4.0097 H CH₃ OH NC(O)C(CH₃)₃ Cl 4.0098 H CH₃ OCH₃ NC(O)C(CH₃)₃ Cl 4.0099 H CH₃ OCH₂CH₃ NC(O)C(CH₃)₃ Cl 4.0100 H CH₃ OC(CH₃)₂ NC(O)C(CH₃)₃ Cl 4.0101 H CH₃ OH CH₂ Br 4.0102 H CH₃ OCH₃ CH₂ Br 4.0103 H CH₃ OCH₂CH₃ CH₂ Br 4.0104 H CH₃ OC(CH₃)₂ CH₂ Br 4.0105 H CH₃ OH CH₂CH₂ Br 4.0106 H CH₃ OCH₃ CH₂CH₂ Br 4.0107 H CH₃ OCH₂CH₃ CH₂CH₂ Br 4.0108 H CH₃ OC(CH₃)₂ CH₂CH₂ Br 4.0109 H CH₃ OH O Br 4.0110 H CH₃ OCH₃ O Br 4.0111 H CH₃ OCH₂CH₃ O Br 4.0112 H CH₃ OC(CH₃)₂ O Br 4.0113 H CH₃ OH NSO₂CH₃ Br 4.0114 H CH₃ OCH₃ NSO₂CH₃ Br 4.0115 H CH₃ OCH₂CH₃ NSO₂CH₃ Br 4.0116 H CH₃ OC(CH₃)₂ NSO₂CH₃ Br 4.0117 H CH₃ OH NC(O)C(CH₃)₃ Br 4.0118 H CH₃ OCH₃ NC(O)O(CH₃)₃ Br 4.0119 H CH₃ OCH₂CH₃ NC(O)O(CH₃)₃ Br 4.0120 H CH₃ OC(CH₃)₂ NC(O)C(CH₃)₃ Br 4.0121 CH₃ CH₃ OH CH₂ H 4.0122 CH₃ CH₃ OCH₃ CH₂ H 4.0123 CH₃ CH₃ OCH₂CH₃ CH₂ H 4.0124 CH₃ CH₃ OC(CH₃)₂ CH₂ H 4.0125 CH₃ CH₃ OH CH₂CH₂ H 4.0126 CH₃ CH₃ OCH₃ CH₂CH₂ H 4.0127 CH₃ CH₃ OCH₂CH₃ CH₂CH₂ H 4.0128 CH₃ CH₃ OC(CH₃)₂ CH₂CH₂ H 4.0129 CH₃ CH₃ OH O H 4.0130 CH₃ CH₃ OCH₃ O H 4.0131 CH₃ CH₃ OCH₂CH₃ O H 4.0132 CH₃ CH₃ OC(CH₃)₂ O H 4.0133 CH₃ CH₃ OH NSO₂CH₃ H 4.0134 CH₃ CH₃ OCH₃ NSO₂CH₃ H 4.0135 CH₃ CH₃ OCH₂CH₃ NSO₂CH₃ H 4.0136 CH₃ CH₃ OC(CH₃)₂ NSO₂CH₃ H 4.0137 CH₃ CH₃ OH NC(O)O(CH₃)₃ H 4.0138 CH₃ CH₃ OCH₃ NC(O)C(CH₃)₃ H 4.0139 CH₃ CH₃ OCH₂CH₃ NC(O)O(CH₃)₃ H 4.0140 CH₃ CH₃ OC(CH₃)₂ NC(O)C(CH₃)₃ H 4.0141 CH₃ CH₃ OH CH₂ Cl 4.0142 CH₃ CH₃ OCH₃ CH₂ Cl see Preparation Example P3 4.0143 CH₃ CH₃ OCH₂CH₃ CH₂ Cl 4.0144 CH₃ CH₃ OC(CH₃)₂ CH₂ Cl 4.0145 CH₃ CH₃ OH CH₂CH₂ Cl 4.0146 CH₃ CH₃ OCH₃ CH₂CH₂ Cl 4.0147 CH₃ CH₃ OCH₂CH₃ CH₂CH₂ Cl 4.0148 CH₃ CH₃ OC(CH₃)₂ CH₂CH₂ Cl 4.0149 CH₃ CH₃ OH O Cl 4.0150 CH₃ CH₃ OCH₃ O Cl 4.0151 CH₃ CH₃ OCH₂CH₃ O Cl 4.0152 CH₃ CH₃ OC(CH₃)₂ O Cl 4.0153 CH₃ CH₃ OH NSO₂CH₃ Cl 4.0154 CH₃ CH₃ OCH₃ NSO₂CH₃ Cl 4.0155 CH₃ CH₃ OCH₂CH₃ NSO₂CH₃ Cl 4.0156 CH₃ CH₃ OC(CH₃)₂ NSO₂CH₃ Cl 4.0157 CH₃ CH₃ OH NO(O)O(CH₃)₃ Cl 4.0158 CH₃ CH₃ OCH₃ NC(O)C(CH₃)₃ Cl 4.0159 CH₃ CH₃ OCH₂CH₃ NC(O)C(CH₃)₃ Cl 4.0160 CH₃ CH₃ OC(CH₃)₂ NC(O)C(CH₃)₃ Cl 4.0161 CH₃ CH₃ OH CH₂ Br 4.0162 CH₃ CH₃ OCH₃ CH₂ Br 4.0163 CH₃ CH₃ OCH₂CH₃ CH₂ Br 4.0164 CH₃ CH₃ OC(CH₃)₂ CH₂ Br 4.0165 CH₃ CH₃ OH CH₂CH₂ Br 4.0166 CH₃ CH₃ OCH₃ CH₂CH₂ Br 4.0167 CH₃ CH₃ OCH₂CH₃ CH₂CH₂ Br 4.0168 CH₃ CH₃ OC(CH₃)₂ CH₂CH₂ Br 4.0169 CH₃ CH₃ OH O Br 4.0170 CH₃ CH₃ OCH₃ O Br 4.0171 CH₃ CH₃ OCH₂CH₃ O Br 4.0172 CH₃ CH₃ OC(CH₃)₂ O Br see Preparation Example P6 4.0173 CH₃ CH₃ OH NSO₂CH₃ Br 4.0174 CH₃ CH₃ OCH₃ NSO₂CH₃ Br 4.0175 CH₃ CH₃ OCH₂CH₃ NSO₂CH₃ Br 4.0176 CH₃ CH₃ OC(CH₃)₂ NSO₂CH₃ Br 4.0177 CH₃ CH₃ OH NC(O)O(CH₃)₃ Br 4.0178 CH₃ CH₃ OCH₃ NC(O)O(CH₃)₃ Br 4.0179 CH₃ CH₃ OCH₂CH₃ NC(O)C(CH₃)₃ Br 4.0180 CH₃ CH₃ OC(CH₃)₂ NC(O)C(CH₃)₃ Br 4.0181 H H OH

H ¹H NMR (300 MHz; CDCl₃) δ 6.30 (sxm, 2H); 3.60 (d, 1H); 3.23 (d, 1H); 2.82 (s, 1H); 0.75 (m, 4H); tautomeric form Db 4.0182 H H OH C(═C(CH₃)₂) H ¹H NMR (300 MHz; CDCl₃) δ 6.82 (sxm, 2H); 4.14 (sxm, 2H); 3.60 (d, 1H); 3.13 (d, 1H); 1.75 (s, 6H); tautomeric form Db 4.0183 H H OH CH₂CH(COOCH₃) H R₇ = Br, see Preparation Example P13 4.0184 H H OH CH₂CH(COOCH₃) H R₇ = CH

TABLE 5 Intermediates of formulae VII: (VII)

No. R₁ R₂ R₃ R₄ Y Xa Physical data 5.0000 H H OCH₃ OCH₃ CH₂ H 5.0001 H H OCH₂CH₃ OCH₂CH₃ CH₂ H 5.0002 H H —OCH₂CH₂O— CH₂ H see Example P8 5.0003 H H OCH₃ OCH₃ O H 5.0004 H H OCH₂CH₃ OCH₂CH₃ O H 5.0005 H H —OCH₂CH₂O— O H 5.0006 H H OCH₃ OCH₃ NSO₂CH₃ H 5.0007 H H OCH₂CH₃ OCH₂CH₃ NSO₂CH₃ H 5.0008 H H —OCH₂CH₂O— NSO₂CH₃ H 5.0009 H H OCH₃ OCH₃ NC(O)C(CH₃)₃ H 5.0010 H H OCH₂CH₃ OCH₂CH₃ NC(O)C(CH₃)₃ H 5.0011 H H —OCH₂CH₂O— NC(O)C(CH₃)₃ H 5.0012 H H OCH₃ OCH₃ CH₂CH₂ H 5.0013 H H OCH₂CH₃ OCH₂CH₃ CH₂CH₂ H 5.0014 H H —OCH₂CH₂O— CH₂CH₂ H 5.0015 H H OCH₃ OCH₃ CH₂ Cl 5.0016 H H OCH₂CH₃ OCH₂CH₃ CH₂ Cl 5.0017 H H —OCH₂CH₂O— CH₂ Cl 5.0018 H H OCH₃ OCH₃ O Cl 5.0019 H H OCH₂CH₃ OCH₂CH₃ O Cl 5.0020 H H —OCH₂CH₂O— O Cl 5.0021 H H OCH₃ OCH₃ NSO₂CH₃ Cl 5.0022 H H OCH₂CH₃ OCH₂CH₃ NSO₂CH₃ Cl 5.0023 H H —OCH₂CH₂O— NSO₂CH₃ Cl 5.0024 H H OCH₃ OCH₃ NC(O)C(CH₃)₃ Cl 5.0025 H H OCH₂CH₃ OCH₂CH₃ NC(O)C(CH₃)₃ Cl 5.0026 H H —OCH₂CH₂O— NC(O)C(CH₃)₃ Cl 5.0027 H H OCH₃ OCH₃ CH₂CH₂ Cl 5.0028 H H OCH₂CH₃ OCH₂CH₃ CH₂CH₂ Cl 5.0029 H H —OCH₂CH₂O— CH₂CH₂ Cl 5.0030 H H OCH₃ OCH₃ CH₂ Br 5.0031 H H OCH₂CH₃ OCH₂CH₃ CH₂ Br 5.0032 H H —OCH₂CH₂O— CH₂ Br 5.0033 H H OCH₃ OCH₃ O Br 5.0034 H H OCH₂CH₃ OCH₂CH₃ O Br 5.0035 H H —OCH₂CH₂O— O Br 5.0036 H H OCH₃ OCH₃ NSO₂CH₃ Br 5.0037 H H OCH₂CH₃ OCH₂CH₃ NSO₂CH₃ Br 5.0038 H H —OCH₂CH₂O— NSO₂CH₃ Br 5.0039 H H OCH₃ OCH₃ NC(O)C(CH₃)₃ Br 5.0040 H H OCH₂CH₃ OCH₂CH₃ NC(O)C(CH₃)₃ Br 5.0041 H H —OCH₂CH₂O— NC(O)C(CH₃)₃ Br 5.0042 H H OCH₃ OCH₃ CH₂CH₂ Br 5.0043 H H OCH₂CH₃ OCH₂CH₃ CH₂CH₂ Br 5.0044 H H —OCH₂CH₂O— CH₂CH₂ Br 5.0045 H CH₃ OCH₃ OCH₃ CH₂ H 5.0046 H CH₃ OCH₂CH₃ OCH₂CH₃ CH₂ H 5.0047 H CH₃ —OCH₂CH₂O— CH₂ H 5.0048 H CH₃ OCH₃ OCH₃ O H 5.0049 H CH₃ OCH₂CH₃ OCH₂CH₃ O H 5.0050 H CH₃ —OCH₂CH₂O— O H 5.0051 H CH₃ OCH₃ OCH₃ NSO₂CH₃ H 5.0052 H CH₃ OCH₂CH₃ OCH₂CH₃ NSO₂CH₃ H 5.0053 H CH₃ —OCH₂CH₂O— NSO₂CH₃ H 5.0054 H CH₃ OCH₃ OCH₃ NC(O)O(CH₃)₃ H 5.0055 H CH₃ OCH₂CH₃ OCH₂CH₃ NC(O)C(CH₃)₃ H 5.0056 H CH₃ —OCH₂CH₂O— NC(O)C(CH₃)₃ H 5.0057 H CH₃ OCH₃ OCH₃ CH₂CH₂ H 5.0058 H CH₃ OCH₂CH₃ OCH₂CH₃ CH₂CH₂ H 5.0059 H CH₃ —OCH₂CH₂O— CH₂CH₂ H 5.0060 H CH₃ OCH₃ OCH₃ CH₂ Cl 5.0061 H CH₃ OCH₂CH₃ OCH₂CH₃ CH₂ Cl 5.0062 H CH₃ —OCH₂CH₂O— CH₂ Cl 5.0063 H CH₃ OCH₃ OCH₃ O Cl 5.0064 H CH₃ OCH₂CH₃ OCH₂CH₃ O Cl 5.0065 H CH₃ —OCH₂CH₂O— O Cl 5.0066 H CH₃ OCH₃ OCH₃ NSO₂CH₃ Cl 5.0067 H CH₃ OCH₂CH₃ OCH₂CH₃ NSO₂CH₃ Cl 5.0068 H CH₃ —OCH₂CH₂O— NSO₂CH₃ Cl 5.0069 H CH₃ OCH₃ OCH₃ NC(O)C(CH₃)₃ Cl 5.0070 H CH₃ OCH₂CH₃ OCH₂CH₃ NC(O)C(CH₃)₃ Cl 5.0071 H CH₃ —OCH₂CH₂O— NC(O)C(CH₃)₃ Cl 5.0072 H CH₃ OCH₃ OCH₃ CH₂CH₂ Cl 5.0073 H CH₃ OCH₂CH₃ OCH₂CH₃ CH₂CH₂ Cl 5.0074 H CH₃ —OCH₂CH₂O— CH₂CH₂ Cl 5.0075 H CH₃ OCH₃ OCH₃ CH₂ Br 5.0076 H CH₃ OCH₂CH₃ OCH₂CH₃ CH₂ Br 5.0077 H CH₃ —OCH₂CH₂O— CH₂ Br 5.0078 H CH₃ OCH₃ OCH₃ O Br 5.0079 H CH₃ OCH₂CH₃ OCH₂CH₃ O Br 5.0080 H CH₃ —OCH₂CH₂O— O Br 5.0081 H CH₃ OCH₃ OCH₃ NSO₂CH₃ Br 5.0082 H CH₃ OCH₂CH₃ OCH₂CH₃ NSO₂CH₃ Br 5.0083 H CH₃ —OCH₂CH₂O— NSO₂CH₃ Br 5.0084 H CH₃ OCH₃ OCH₃ NC(O)O(CH₃)₃ Br 5.0085 H CH₃ OCH₂CH₃ OCH₂CH₃ NC(O)C(CH₃)₃ Br 5.0086 H CH₃ —OCH₂CH₂O— NC(O)O(CH₃)₃ Br 5.0087 H CH₃ OCH₃ OCH₃ CH₂CH₂ Br 5.0088 H CH₃ OCH₂CH₃ OCH₂CH₃ CH₂CH₂ Br 5.0089 H CH₃ —OCH₂CH₂O— CH₂CH₂ Br 5.0090 CH₃ CH₃ OCH₃ OCH₃ CH₂ H 5.0091 CH₃ CH₃ OCH₂CH₃ OCH₂CH₃ CH₂ H 5.0092 CH₃ CH₃ —OCH₂CH₂O— CH₂ H 5.0093 CH₃ CH₃ OCH₃ OCH₃ O H see Example P5 5.0094 CH₃ CH₃ OCH₂CH₃ OCH₂CH₃ O H 5.0095 CH₃ CH₃ —OCH₂CH₂O— O H 5.0096 CH₃ CH₃ OCH₃ OCH₃ NSO₂CH₃ H 5.0097 CH₃ CH₃ OCH₂CH₃ OCH₂CH₃ NSO₂CH₃ H 5.0098 CH₃ CH₃ —OCH₂CH₂O— NSO₂CH₃ H 5.0099 CH₃ CH₃ OCH₃ OCH₃ NC(O)O(CH₃)₃ H 5.0100 CH₃ CH₃ OCH₂CH₃ OCH₂CH₃ NC(O)O(CH₃)₃ H 5.0101 CH₃ CH₃ —OCH₂CH₂O— NC(O)O(CH₃)₃ H 5.0102 CH₃ CH₃ OCH₃ OCH₃ CH₂CH₂ H 5.0103 CH₃ CH₃ OCH₂CH₃ OCH₂CH₃ CH₂CH₂ H 5.0104 CH₃ CH₃ —OCH₂CH₂O— CH₂CH₂ H 5.0105 CH₃ CH₃ OCH₃ OCH₃ CH₂ Cl 5.0106 CH₃ CH₃ OCH₂CH₃ OCH₂CH₃ CH₂ Cl 5.0107 CH₃ CH₃ —OCH₂CH₂O— CH₂ Cl 5.0108 CH₃ CH₃ OCH₃ OCH₃ O Cl see Example P3 5.0109 CH₃ CH₃ OCH₂CH₃ OCH₂CH₃ O Cl 5.0110 CH₃ CH₃ —OCH₂CH₂O— O Cl 5.0111 CH₃ CH₃ OCH₃ OCH₃ NSO₂CH₃ Cl 5.0112 CH₃ CH₃ OCH₂CH₃ OCH₂CH₃ NSO₂CH₃ Cl 5.0113 CH₃ CH₃ —OCH₂CH₂O— NSO₂CH₃ Cl 5.0114 CH₃ CH₃ OCH₃ OCH₃ NC(O)O(CH₃)₃ Cl 5.0115 CH₃ CH₃ OCH₂CH₃ OCH₂CH₃ NC(O)O(CH₃)₃ Cl 5.0116 CH₃ CH₃ —OCH₂CH₂O— NC(O)O(CH₃)₃ Cl 5.0117 CH₃ CH₃ OCH₃ OCH₃ CH₂CH₂ Cl 5.0118 CH₃ CH₃ OCH₂CH₃ OCH₂CH₃ CH₂CH₂ Cl 5.0119 CH₃ CH₃ —OCH₂CH₂O— CH₂CH₂ Cl 5.0120 CH₃ CH₃ OCH₃ OCH₃ CH₂ Br 5.0121 CH₃ CH₃ OCH₂CH₃ OCH₂CH₃ CH₂ Br 5.0122 CH₃ CH₃ —OCH₂CH₂O— CH₂ Br 5.0123 CH₃ CH₃ OCH₃ OCH₃ O Br 5.0124 CH₃ CH₃ OCH₂CH₃ OCH₂CH₃ O Br 5.0125 CH₃ CH₃ —OCH₂CH₂O— O Br 5.0126 CH₃ CH₃ OCH₃ OCH₃ NSO₂CH₃ Br 5.0127 CH₃ CH₃ OCH₂CH₃ OCH₂CH₃ NSO₂CH₃ Br 5.0128 CH₃ CH₃ —OCH₂CH₂O— NSO₂CH₃ Br 5.0129 CH₃ CH₃ OCH₃ OCH₃ NC(O)C(CH₃)₃ Br 5.0130 CH₃ CH₃ OCH₂CH₃ OCH₂CH₃ NC(O)O(CH₃)₃ Br 5.0131 CH₃ CH₃ —OCH₂CH₂O— NC(O)C(CH₃)₃ Br 5.0132 CH₃ CH₃ OCH₃ OCH₃ CH₂CH₂ Br 5.0133 CH₃ CH₃ OCH₂CH₃ OCH₂CH₃ CH₂CH₂ Br 5.0134 CH₃ CH₃ —OCH₂CH₂O— CH₂CH₂ Br 5.0135 H H —OCH₂CH₂O—

Cl Amorphous crystals

TABLE 6 Intermediates of formula VI: (VI)

No. A₁ A₂ R₁ R₂ Y Xa Physical data 6.0000 CH CH H H C(═CH(OAc)) Cl major isomer I: ¹H NMR (300 MHz: CDCl₃) δ 7.12 (s, 1H); 6.77 (dxd, 1H); 6.35 (dxd, 1H); 4.02 (d, 1H); 3.95 (d, 1H); 2.18 (s, 3H). 6.0001 CH CH H H C(═CH(OAc)) Cl minor isomer II: ¹H NMR (300 MHz; CDCl₃) δ 7.14 (s, 1H); 6.84 (dxd, 1H); 6.29 (dxd, 1H); 4.55 (d, 1H); 3.54 (d, 1H); 2.19 (s, 3H).

BIOLOGICAL EXAMPLES Example B1 Herbicidal Action Prior to Emergence of the Plants (Pre-Emergence Action)

Monocotyledonous and dicotyledonous test plants are sown in standard soil in plastic pots. Immediately after sowing, the test compounds, in the form of an aqueous suspension (prepared from a 25% wettable powder (Example F3, b) according to WO 97/34485) or in the form of an emulsion (prepared from a 25% emulsifiable concentrate (Example F1, c)), are applied by spraying in a concentration corresponding to 125 g or 250 g of active ingredient/ha (500 litres of water/ha). The test plants are then grown in a greenhouse under optimum conditions. After a test duration of 3 weeks, the test is evaluated in accordance with a scale of ten ratings (10=total damage, 0=no action). Ratings of from 10 to 6 (especially from 10 to 8) indicate good to very good herbicidal action. The compounds of formula I exhibit strong herbicidal action in this test. Examples of the good herbicidal action of the compounds are given in Table B1: TABLE B1 Pre-emergence herbicidal action: Ex. No. gr/ha Panicum Echinochloa Abutilon Amaranthus Chenopodium Kochia 1.0301 250 7 7 7 8 9 8 1.0411 250 10 9 10 10 10 10

Example B2 Post-Emergence Herbicidal Action

In a greenhouse, monocotyledonous and dicotyledonous test plants are grown in standard soil in plastic pots and at the 4- to 6-leaf stage are sprayed with an aqueous suspension of the test compounds of formula I prepared from a 25% wettable powder (Example F3, b) according to WO 97/34485) or with an emulsion of the test compounds of formula I prepared from a 25% emulsifiable concentrate (Example F1, c) according to WO 97/34485), in a concentration corresponding to 125 g or 250 g of active ingredient/ha (500 litres of water/ha). The test plants are then grown on in a greenhouse under optimum conditions. After a test duration of about 18 days, the test is evaluated in accordance with a scale of ten ratings (10=total damage, 0=no action). Ratings of from 10 to 6 (especially from 10 to 7) indicate good to very good herbicidal action. The compounds of formula I exhibit a strong herbicidal action in this test. Examples of the good herbicidal action of the compounds are given in Table B2: TABLE B2 Post-emergence herbicidal action: Ex. No. gr/ha Abutilon Ipomea Amaranthus Chenopodium Stellaria Abutilon 1.0301 250 9 8 8 8 8 8 1.0411 250 9 10 9 10 9 9 1.1153 250 7 8 7 8 10 8

Example B3 Comparison Test with a Compound from the Prior Art: Post-Emergence Herbicidal Action

The post-emergence herbicidal action of compound No. 1.0411 according to the invention is compared with compound “A” from WO 01/94339:

TABLE B3 Post-emergence action: Ex. No. gr/ha Brachiaria Rottboelia Sida Polygonum Sinapis Galium 1.0411 15 10 3 8 8 8 6 A 15 4 0 7 5 6 5

It can be seen from Table B3 that compound No. 1.0411 according to the invention at a rate of application of 15 g/ha exhibits considerably better herbicidal action on the weeds than compound “A” from the prior art. This enhanced action was not to be expected in view of the structural similarity of the compounds. 

1. A compound of formula I

wherein Y is oxygen, NR_(4a), sulfur, sulfonyl, sulfinyl, C(O), C(═NR_(4b)), C(═CR_(6a)R_(6b)) or a C₁-C₄alkylene or C₂-C₄alkenylene chain, which may be interrupted by oxygen, NR_(5a), sulfur, sulfonyl, sulfinyl, C(O) or C(═NR_(5b)) and/or mono- or poly-substituted by R₆; A₁ is nitrogen or CR₇; A₂ is nitrogen or CR₈; R₁, R₂, R₆, R₇ and R₈ are each independently of the others hydrogen, hydroxy, mercapto, NO₂, cyano, halogen, formyl, oxyiminomethylene, C₁-C₆alkoxyiminomethylene, C₁-C₆alkyl, C₁-C₆haloalkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-C₆alkynyl, C₂-C₆haloalkynyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₃-C₆alkenyloxy, C₃-C₆alkynyloxy, C₃-C₆oxacycloalkyl, C₃-C₆thiacycloalkyl, C₃-C₆dioxacycloalkyl, C₃-C₆dithiacycloalkyl, C₃-C₆oxathiacycloalkyl, C₁-C₆alkoxycarbonyl, C₁-C₆alkylcarbonyl, C₁-C₆alkoxycarbonyloxy, C₁-C₆alkylcarbonyloxy, C₁-C₆alkylthio, C₁-C₆-alkylsulfonyl, C₁-C₆alkylsulfinyl, NR₉R₁₀, C₃-C₆cycloalkyl, tri(C₁-C₆alkyl)silyl, di(C₁-C₆alkyl)-phenylsilyl, tri(C₁-C₆alkyl)silyloxy, di(C₁-C₆alkyl)phenylsilyloxy or Ar₁; or R₁, R₂, R₆, R₇, R₈ are each independently of the others a C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl or C₃-C₆cycloalkyl group, which may be interrupted by oxygen, sulfur, sulfonyl, sulfinyl, —NR₁₁— or —C(O)— and/or mono-, di- or tri-substituted by hydroxy, mercapto, NO₂, cyano, halogen, formyl, C₁-C₆alkoxy, C₃-C₆alkenyloxy, C₃-C₆alkynyloxy, C₁-C₆haloalkoxy, C₁-C₂alkoxy-C₁-C₂alkoxy, C₁-C₄alkoxycarbonyloxy, C₁-C₄alkylcarbonyloxy, C₁-C₄alkoxycarbonyl, C₁-C₄alkylcarbonyl, C₁-C₆alkylthio, C₁-C₆alkylsulfinyl, C₁-C₆alkylsulfonyl, NR₁₂R₁₃, C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl, C₃-C₆cycloalkyl, tri(C₁-C₆alkyl)silyl, tri(C₁-C₆alkyl)silyloxy or Ar₂; or two substituents R₆ at the same carbon atom together form a —CH₂O— or a C₂-C₅alkylene chain, which may be interrupted once or twice by oxygen, sulfur, sulfinyl or sulfonyl and/or mono- or poly-substituted by R_(6c), with the proviso that two hetero atoms may not be located next to one another; or two substituents R₆ at different carbon atoms together form an oxygen bridge or a C₁-C₄alkylene chain, which may in turn be substituted by R_(6c); or R₇ and R₈ together form a —CH₂CH═CH—, —OCH═CH— or —CH═CH—CH═CH— bridge or a C₃-C₄alkylene chain, which may be interrupted by oxygen or —S(O)_(n1)— and/or mono- or poly-substituted by R_(6d); R₃ is hydroxy, halogen, mercapto, C₁-C₈alkylthio, C₁-C₈alkylsulfinyl, C₁-C₈alkylsulfonyl, C₁-C₈haloalkylthio, C₁-C₈haloalkylsulfinyl, C₁-C₈haloalkylsulfonyl, C₁-C₄alkoxy-C₁-C₄alkylthio, C₁-C₄alkoxy-C₁-C₄alkylsulfinyl, C₁-C₄alkoxy-C₁-C₄alkylsulfonyl, C₃-C₈alkenylthio, C₃-C₈-alkynylthio, C₁-C₄alkylthio-C₁-C₄alkylthio, C₃-C₄alkenylthio-C₁-C₄alkylthio, C₁-C₄alkoxycarbonyl-C₁-C₄alkylthio, C₁-C₄alkoxycarbonyl-C₁-C₄alkylsulfinyl, C₁-C₄alkoxycarbonyl-C₁-C₄alkylsulfonyl, C₃-C₈cycloalkylthio, C₃-C₈cycloalkylsulfinyl, C₃-C₈cycloalkylsulfonyl, phenyl-C₁-C₄alkylthio, phenyl-C₁-C₄alkylsulfinyl, phenyl-C₁-C₄alkylsulfonyl, S(O)n₁—Ar₃, phenylthio, phenylsulfinyl, phenylsulfonyl, it being possible for the phenyl-containing groups to be substituted by one or more C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₄alkoxycarbonyl, halogen, cyano, hydroxy or nitro groups; or R₃ is O⁻M⁺, wherein M⁺ is an alkali metal cation or an ammonium cation; Q is a radical

p₁, p₂ and p₃ are 0 or 1; m₁, m₂ and m₃ are 1, 2 or 3; X₁, X₂ and X₃ are hydroxy, halogen, C₁-C₆alkyl, C₁-C₆haloalkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-C₆alkynyl, C₂-C₆haloalkynyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₁-C₆alkylthio, C₁-C₆alkylsulfinyl, C₁-C₆alkylsulfonyl, C₁-C₆haloalkylthio, C₁-C₆haloalkylsulfinyl or C₁-C₆haloalkylsulfonyl; Z₁, Z₂ and Z₃ are C₁-C₆alkyl which is substituted by the following substituents: C₃-C₄cycloalkyl or C₃-C₄cycloalkyl substituted by halogen, C₁-C₆alkyl, C₁-C₃alkoxy or C₁-C₃alkoxy-C₁-C₃alkyl; oxiranyl or oxiranyl substituted by C₁-C₆alkyl or C₁-C₃alkoxy-C₁-C₃alkyl; 3-oxetanyl or 3-oxetanyl substituted by C₁-C₆alkyl, C₁-C₃alkoxy or C₁-C₃alkoxy-C₁-C₃alkyl; 3-oxetanyloxy or 3-oxetanyloxy substituted by C₁-C₆alkyl, C₁-C₃alkoxy or C₁-C₃alkoxy-C₁-C₃-alkyl; C₃-C₆cycloalkyloxy or C₃-C₄cycloalkyloxy substituted by halogen, C₁-C₆alkyl, C₁-C₃-alkoxy or C₁-C₃alkoxy-C₁-C₃alkyl; C₁-C₆haloalkoxy; C₁-C₆alkylsulfonyloxy; C₁-C₆haloalkylsulfonyloxy; phenylsulfonyloxy; benzylsulfonyloxy, benzoyloxy; phenoxy; phenylthio; phenyl-sulfinyl; phenylsulfonyl; Ar₁₀; OAr₁₂; tri(C₁-C₆alkyl)silyl or tri(C₁-C₆alkyl)silyloxy, it being possible for the phenyl-containing groups to be mono- or poly-substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano, hydroxy or nitro; or Z₁, Z₂ and Z₃ are 3-oxetanyl; 3-oxetanyl substituted by C₁-C₃alkoxy, C₁-C₃alkoxy-C₁-C₃alkyl or C₁-C₆alkyl; C₃-C₆cycloalkyl substituted by halogen, C₁-C₃alkyl or C₁-C₃alkoxy-C₁-C₃alkyl; tri(C₁-C₆alkyl)silyl; tri(C₁-C₆alkyl)silyloxy or CH═P(phenyl)₃; or Z₁, Z₂ and Z₃ are a C₁-C₆alkyl, C₂-C₆alkenyl or C₂-C₆alkynyl group, which is interrupted by oxygen, —O(CO)—, —(CO)O—, —O(CO)O—, —N(R₁₄)O—, —ONR₁₅—, sulfur, sulfinyl, sulfonyl, —SO₂NR₁₆—, —NR₁₇SO₂— or —NR₁₈— and is mono- or poly-substituted by L₁; it also being possible for L₁ to be bonded at the terminal carbon atom of the C₁-C₆alkyl, C₂-C₆alkenyl or C₂-C₆alkynyl group; or Z₁, Z₂ and Z₃ are hydrogen, hydroxy, mercapto, NO₂, cyano, halogen, formyl, C₁-C₆alkyl, C₁-C₆haloalkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-C₆alkynyl, C₂-C₆haloalkynyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₁-C₆alkoxycarbonyl, C₁-C₆alkylcarbonyl, C₁-C₆alkylthio, C₁-C₆alkylsulfonyl, C₁-C₆alkylsulfinyl, NR₂₂R₂₃, phenyl which may be mono- or poly-substituted by C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano, hydroxy or nitro, C₃-C₆cycloalkyl, C₅-C₆cycloalkyl substituted by C₁-C₃alkoxy, C₁-C₃alkoxy-C₁-C₃alkyl or C₁-C₆alkyl, or Ar₅, O—Ar₆, N(R₂₄)Ar₇ or S(O)n₆Ar₈; L₁ is hydrogen, halogen, hydroxy, amino, formyl, nitro, cyano, mercapto, carbamoyl, P(O)(OC₁—C₆alkyl)₂, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₁-C₆alkoxycarbonyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-C₆alkynyl, C₂-C₆haloalkynyl, C₃-C₆cycloalkyl, halo-substituted C₃-C₆cycloalkyl, C₃-C₆alkenyloxy, C₃-C₆alkynyloxy, C₃-C₆haloalkenyloxy, cyano-C₁-C₆alkoxy, C₁-C₆alkoxy-C₁-C₆alkoxy, C₁-C₆alkylthio-C₁-C₆alkoxy, C₁-C₆alkylsulfinyl-C₁-C₆alkoxy, C₁-C₆-alkylsulfonyl-C₁-C₆alkoxy, C₁-C₆alkoxycarbonyl-C₁-C₆alkoxy, C₁-C₆alkylcarbonyloxy-C₁-C₆-alkylcarbonyl, C₁-C₆alkylthio, C₁-C₆alkylsulfinyl, C₁-C₆alkylsulfonyl, C₁-C₆haloalkylthio, C₁-C₆haloalkylsulfinyl, C₁-C₆haloalkylsulfonyl or oxiranyl, which may in turn be substituted by C₁-C₆alkyl, C₁-C₃alkoxy or C₁-C₃alkoxy-C₁-C₃alkyl, or (3-oxetanyl)-oxy, which may in turn be substituted by C₁-C₆alkyl, C₁-C₃alkoxy or C₁-C₃alkoxy-C₁-C₃alkyl, or benzoyloxy, benzyloxy, benzylthio, benzylsulfinyl, benzylsulfonyl, C₁-C₆alkylamino, di(C₁-C₆alkyl)amino, R₁₉S(O)₂O—, R₂₀N(R₂₁)SO₂—, rhodano, phenyl, phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl, Ar₄ or OAr₁₁, it being possible for the phenyl-containing groups in turn to be substituted by one or more C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy, C₁-C₃haloalkoxy, halogen, cyano, hydroxy or nitro groups; R_(4a) and R_(5a) are each independently of the other hydrogen, C₁-C₆alkyl, C₁-C₆haloalkyl, cyano, formyl, C₁-C₆alkylcarbonyl, C₁-C₆alkoxycarbonyl, carbamoyl, C₁-C₆alkylaminocarbonyl, di(C₁-C₆alkylamino)carbonyl, di(C₁-C₆alkylamino)sulfonyl, C₃-C₆cycloalkylcarbonyl, C₁-C₆-alkylsulfonyl, phenylcarbonyl, phenylaminocarbonyl or phenylsulfonyl, it being possible for the phenyl groups to be mono- or poly-substituted by C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆-alkoxy, C₁-C₆haloalkoxy, halogen, cyano, hydroxy or nitro; R_(4b) and R_(5b) are each independently of the other hydroxy, C₁-C₆alkoxy, C₃-C₆alkenyloxy, C₃-C₆alkynyloxy or benzyloxy, it being possible for the benzyl group to be mono- or poly-substituted by C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, halogen, cyano, hydroxy or nitro; R₉, R₁₁, R₁₃, R₁₆, R₁₇, R₁₈, R₂₀, R₂₃ and R₂₄ are each independently of the others hydrogen, C₁-C₆alkyl, Ar₉, C₁-C₆haloalkyl, C₁-C₆alkylcarbonyl, C₁-C₆alkoxycarbonyl, C₁-C₆alkylsulfonyl, phenyl, it being possible for the phenyl group in turn to be mono- or poly-substituted by C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, halogen, cyano, hydroxy or nitro; R_(6a) is hydrogen, C₁-C₆alkyl or C₁-C₆alkylcarbonyl; or together with R_(6b) is a C₂-C₅alkylene chain; R_(6b), R_(6d), R₁₀, R₁₂ and R₂₂ are each independently of the others hydrogen or C₁-C₆alkyl; R_(6c), R₁₄, R₁₅, R₁₉ and R₂₁, are each independently of the others C₁-C₆alkyl or C₁-C₆haloalkyl; Ar₁, Ar₂, Ar₃, Ar₄, Ar₅, Ar₆, Ar₇, Ar₈, Ar₉, Ar₁₀, Ar₁₁ and Ar₁₂ are each independently of the others a five- to ten-membered, monocyclic or fused bicyclic ring system, which may be aromatic, partially saturated or fully saturated and may contain from 1 to 4 hetero atoms selected from nitrogen, oxygen, sulfur, C(O) and C(═NR₂₅), and each ring system may contain not more than two oxygen atoms, not more than two sulfur atoms, not more than two C(O) groups and not more than one C(═NR₂₅) group, and each ring system may itself be mono- or poly-substituted by C₁-C₆alkyl, C₁-C₆haloalkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-C₆alkynyl, C₂-C₆haloalkynyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₃-C₆alkenyloxy, C₃-C₆alkynyloxy, mercapto, amino, hydroxy, C₁-C₆alkylthio, C₁-C₆haloalkylthio, C₃-C₆alkenylthio, C₃-C₆-haloalkenylthio, C₃-C₆alkynylthio, C₁-C₃alkoxy-C₁-C₃alkylthio, C₁-C₄alkylcarbonyl-C₁-C₃alkylthio, C₁-C₄alkoxycarbonyl-C₁-C₃alkylthio, cyano-C₁-C₃alkylthio, C₁-C₆alkylsulfinyl, C₁-C₆haloalkylsulfinyl, C₁-C₆alkylsulfonyl, C₁-C₆haloalkylsulfonyl, aminosulfonyl, C₁-C₂alkylaminosulfonyl, N,N-di(C₁-C₂alkyl)aminosulfonyl, di(C₁-C₄alkyl)amino, halogen, cyano, nitro or phenyl, it being possible for the phenyl group in turn to be substituted by hydroxy, C₁-C₆-alkylthio, C₁-C₆haloalkylthio, C₃-C₆alkenylthio, C₃-C₆haloalkenylthio, C₃-C₆alkynylthio, C₁-C₃alkoxy-C₁-C₃alkylthio, C₁-C₄alkylcarbonyl-C₁-C₃alkylthio, C₁-C₄alkoxycarbonyl-C₁-C₃-alkylthio, cyano-C₁-C₃alkylthio, C₁-C₆alkylsulfinyl, C₁-C₆haloalkylsulfinyl, C₁-C₆alkylsulfonyl, C₁-C₆haloalkylsulfonyl, aminosulfonyl, C₁-C₂alkylaminosulfonyl, N,N-di(C₁-C₂alkyl)aminosulfonyl, di(C₁-C₄alkyl)amino, halogen, cyano or nitro, and the substituents at the nitrogen atom in the heterocyclic ring being other than halogen, and two oxygen atoms not being located next to one another; R₂₅ is hydrogen, hydroxy, C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy, C₁-C₆alkylcarbonyl, C₁-C₆alkoxycarbonyl or C₁-C₆alkylsulfonyl; and n₁ is 0, 1 or 2; and n₆ is 0, 1 or 2; or an agronomically acceptable salt/isomer/enantiomer/tautomer of such a compound.
 2. A compound of formula Da

wherein Y, R₁, R₂, A₁ and A₂ are as defined for formula I in claim
 1. 3. A compound of formula Db

wherein A₁, A₂, R₁, R₂ and Y are as defined for formula I in claim 1, Xa is hydrogen, chlorine or bromine and R₃ is hydroxy or C₁-C₆alkoxy, with the exception of the compounds 3-chloro-8-oxa-bicyclo[3.2.1]oct-6-ene-2,4-dione; 3-chloro-bicyclo[3.2.1]oct-6-ene-2,4-dione; 3-chloro-4-hydroxy-bicyclo[3.2.1]octa-3,6-dien-2-one; 3,4-dibromo-8-oxa-bicyclo[3.2.1]octa-3,6-dien-2-one; 3,4dibromo-1,5-dimethyl-8-oxa-bicyclo[3.2.1]octa-3,6-dien-2-one; 3,4-dibromo-bicyclo[3.2.1]octa-3,6-dien-2-one; 3,4-dichloro-8-oxa-bicyclo[3.2.1]octa-3,6-dien-2-one; 3,4-dichloro-bicyclo[3.2.1]octa-3,6-dien-2-one and 7,8-dibromo-5,9-dihydro-5,9-methano-benzo-cyclohepten-6-one.
 4. A compound of formula VII

wherein A₁, A₂, R₁, R₂, Y are as defined for formula I in claim 1, Xa is hydrogen, chlorine or bromine and R₃a is C₁-C₆alkyl or two R₃a together are —CH₂CH₂—.
 5. A herbicidal and plant-growth-inhibiting composition, comprising a herbicidally effective amount of a compound of formula I according to claim 1 on an inert carrier.
 6. A method of controlling undesired plant growth, which method comprises applying a compound of formula I according to claim 5, or a composition comprising such a compound, in a herbicidally effective amount to a plant or to the locus thereof.
 7. A method of inhibiting plant growth, which method comprises applying a compound of formula I according to claim 5, or a composition comprising such a compound, in a herbicidally effective amount to a plant or to the locus thereof. 